技术领域technical field
本发明涉及一种高分子过滤膜技术领域，尤其涉及一种超滤膜或纳滤膜及其制备方法。The invention relates to the technical field of polymer filtration membranes, in particular to an ultrafiltration membrane or nanofiltration membrane and a preparation method thereof.
背景技术Background technique
超滤膜，是一种孔径规格一致、额定孔径范围为1～20纳米、截留分子量范围在1000～1000000的微孔过滤膜。目前常见超滤膜有聚砜、聚醚砜、聚丙烯腈、聚偏氟乙烯、聚氯乙烯、聚丙烯等材质的。纳滤膜是具有纳米级的孔径，其截留分子量为200～1000。常见的纳滤膜有聚酰胺、聚乙烯醇、磺化聚砜、磺化聚醚砜、醋酸纤维素及其衍生物等材质的。现有的超滤膜和纳滤膜一般适用于水环境中，然而对于有机溶剂体系，现有的超滤膜或纳滤膜在其中会发生溶胀，甚至溶解。Ultrafiltration membrane is a microporous filtration membrane with uniform pore size, rated pore size range of 1-20 nanometers, and molecular weight cut-off range of 1,000-1,000,000. At present, common ultrafiltration membranes are made of polysulfone, polyethersulfone, polyacrylonitrile, polyvinylidene fluoride, polyvinyl chloride, polypropylene and other materials. The nanofiltration membrane has a nano-scale pore size, and its molecular weight cut-off is 200-1000. Common nanofiltration membranes are made of polyamide, polyvinyl alcohol, sulfonated polysulfone, sulfonated polyethersulfone, cellulose acetate and its derivatives. Existing ultrafiltration membranes and nanofiltration membranes are generally suitable for use in water environments. However, for organic solvent systems, existing ultrafiltration membranes or nanofiltration membranes will swell or even dissolve in them.
为了能够适用于有机溶剂体系，现有技术开发了耐有机溶剂的超滤膜或纳滤膜。通常耐有机溶剂的超滤膜或纳滤膜是无机膜，如陶瓷膜，但陶瓷膜价格高；而且由于陶瓷本身的性质所决定，无法制成卷式膜和中空纤维膜，使得陶瓷膜元件形式单一；再者现有工艺制备得到的陶瓷纳滤膜性能稳定差。为了得到性能稳定且多元化的膜元件，现有技术致力于具有耐有机溶剂性能的有机超滤膜或纳滤膜。In order to be applicable to organic solvent systems, organic solvent-resistant ultrafiltration membranes or nanofiltration membranes have been developed in the prior art. Usually the ultrafiltration membrane or nanofiltration membrane resistant to organic solvents is an inorganic membrane, such as a ceramic membrane, but the price of the ceramic membrane is high; The form is single; moreover, the performance of the ceramic nanofiltration membrane prepared by the existing technology is poor. In order to obtain stable and diversified membrane elements, the prior art is dedicated to organic ultrafiltration membranes or nanofiltration membranes with resistance to organic solvents.
现有技术中适合于耐溶剂有机膜制备的聚合物材料有聚酰亚胺、硅橡胶、聚丙烯腈、聚亚胺酯以及其他交联聚合物等，其中，聚酰亚胺以其良好热稳定性和化学稳定性成为最重要的耐溶剂膜材料之一。如房昺等通过两步法制备了一种聚酰亚胺膜（PI膜），并采用正己烷、环己酮、甲醇、四氢呋喃、N-甲基吡咯烷酮、乙酸乙酯、盐酸（pH值=1）、氢氧化钠溶液（pH值=10）不同的溶剂，研究了其耐溶剂性能，结果显示，在酸性溶液中的PI膜前30天截留率基本没有下降，60天后开始下降明显；在碱性溶液中的PI膜截留率从15天就开始明显下降；而在其他溶剂体系中的PI膜，随着浸泡时间的增长，截留率虽有下降，但超过120天后大部分体系中的PI膜仍可发挥分离效果，说明此PI膜具有良好的耐有机溶剂性（房昺.聚酰亚胺耐溶剂纳滤膜的制备与性能研究[M],2011年6月），但在酸性和碱性环境中不稳定。Polymer materials suitable for the preparation of solvent-resistant organic membranes in the prior art include polyimide, silicone rubber, polyacrylonitrile, polyurethane and other cross-linked polymers, among which polyimide is characterized by its good thermal Stability and chemical stability become one of the most important solvent-resistant membrane materials. For example, Fang Bing and others prepared a polyimide film (PI film) by a two-step method, and used n-hexane, cyclohexanone, methanol, tetrahydrofuran, N-methylpyrrolidone, ethyl acetate, hydrochloric acid (pH = 1) Different solvents of sodium hydroxide solution (pH value = 10) were studied for their solvent resistance. The results showed that the rejection rate of the PI membrane in the acidic solution basically did not decrease in the first 30 days, and began to decrease significantly after 60 days; The rejection rate of the PI membrane in the alkaline solution began to decrease significantly from 15 days; while the rejection rate of the PI membrane in other solvent systems decreased with the increase of the soaking time, but after more than 120 days, the PI membrane in most systems The membrane can still play a separation effect, indicating that this PI membrane has good resistance to organic solvents (Fang Bing. Preparation and performance of polyimide solvent-resistant nanofiltration membrane [M], June 2011), but in acidic and Unstable in alkaline environment.
发明内容Contents of the invention
有鉴于此，本发明的目的在于提供一种超滤膜或纳滤膜及其制备方法，本发明提供的方法制备的超滤膜或纳滤膜在酸性和碱性环境中具有良好的稳定性。In view of this, the object of the present invention is to provide a kind of ultrafiltration membrane or nanofiltration membrane and preparation method thereof, the ultrafiltration membrane or nanofiltration membrane prepared by the method provided by the invention has good stability in acidic and alkaline environment .
本发明提供一种超滤膜或纳滤膜的制备方法，包括以下步骤：The invention provides a kind of preparation method of ultrafiltration membrane or nanofiltration membrane, comprises the following steps:
a）制备聚合物溶液，所述聚合物具有式（I）或式（II）所示结构：a) preparing a polymer solution, the polymer having a structure shown in formula (I) or formula (II):
其中，1≤x≤20；1≤y≤20；0≤z≤1；1≤n≤10000；Among them, 1≤x≤20; 1≤y≤20; 0≤z≤1; 1≤n≤10000;
其中，R1、R2、R3、R4、R5、R6、R7和R8至少有一个为-CH2-N(CH3)2；0≤z≤1；1≤n≤10000；Among them, at least one of R1 , R2 , R3 , R4 , R5 , R6 , R7 and R8 is -CH2 -N(CH3 )2 ; 0≤z≤1; 1≤n≤ 10000;
所述式（II）中Ar具有式(101)～式(105)所示结构中的任意一种：Ar in the formula (II) has any one of the structures shown in formula (101) to formula (105):
b）将所述步骤a）的聚合物溶液与交联剂混合，进行交联反应，得到制膜液，所述交联反应的温度为20℃～150℃；b) mixing the polymer solution in the step a) with a cross-linking agent to perform a cross-linking reaction to obtain a film-forming liquid, and the temperature of the cross-linking reaction is 20°C to 150°C;
c）将所述步骤b）的制膜液进行制膜，得到超滤膜或纳滤膜。c) The membrane-forming solution in the step b) is used to form a membrane to obtain an ultrafiltration membrane or a nanofiltration membrane.
优选地，所述交联剂为具有式（III）、式（IV）和式（V）所示结构的化合物中的一种或多种：Preferably, the crosslinking agent is one or more of the compounds having the structures shown in formula (III), formula (IV) and formula (V):
其中，X1、X2、X3、X4或X5独立地选自Cl、Br或I；Wherein, X1 , X2 , X3 , X4 or X5 are independently selected from Cl, Br or I;
式（IV）中，1≤m≤20。In formula (IV), 1≤m≤20.
优选地，所述聚合物与交联剂的质量比为1:0.0001～0.1。Preferably, the mass ratio of the polymer to the crosslinking agent is 1:0.0001-0.1.
优选地，所述交联反应的时间为10min～300min。Preferably, the time for the crosslinking reaction is 10 minutes to 300 minutes.
优选地，所述步骤c）后还包括以下步骤：Preferably, after step c), the following steps are also included:
将所述步骤c）得到的超滤膜或纳滤膜与交联剂混合，进行交联反应。The ultrafiltration membrane or nanofiltration membrane obtained in the step c) is mixed with a crosslinking agent to perform a crosslinking reaction.
本发明还提供一种超滤膜或纳滤膜的制备方法，包括以下步骤：The present invention also provides a preparation method of ultrafiltration membrane or nanofiltration membrane, comprising the following steps:
a）制备聚合物溶液，所述聚合物具有式（I）或式（II）所示结构：a) preparing a polymer solution, the polymer having a structure shown in formula (I) or formula (II):
其中，1≤x≤20；1≤y≤20；0≤z≤1；1≤n≤10000；Among them, 1≤x≤20; 1≤y≤20; 0≤z≤1; 1≤n≤10000;
其中，R1、R2、R3、R4、R5、R6、R7和R8至少有一个为-CH2-N(CH3)2；0≤z≤1；1≤n≤10000；Among them, at least one of R1 , R2 , R3 , R4 , R5 , R6 , R7 and R8 is -CH2 -N(CH3 )2 ; 0≤z≤1; 1≤n≤ 10000;
所述式（II）中Ar具有式(101)～式(105)所示结构中的任意一种：Ar in the formula (II) has any one of the structures shown in formula (101) to formula (105):
b）将所述步骤a）的聚合物溶液进行制膜，得到聚合物膜；b) forming a film from the polymer solution in step a) to obtain a polymer film;
c）将所述步骤b）得到的聚合物膜与交联剂混合，进行交联反应，所述交联反应的温度为20℃～150℃，得到超滤膜或纳滤膜。c) mixing the polymer membrane obtained in the step b) with a cross-linking agent to perform a cross-linking reaction, the temperature of the cross-linking reaction being 20° C. to 150° C. to obtain an ultrafiltration membrane or a nanofiltration membrane.
优选地，所述交联剂为具有式（III）、式（IV）和式（V）所示结构的化合物中的一种或多种：Preferably, the crosslinking agent is one or more of the compounds having the structures shown in formula (III), formula (IV) and formula (V):
其中，X1、X2、X3、X4或X5独立地选自Cl、Br或I；Wherein, X1 , X2 , X3 , X4 or X5 are independently selected from Cl, Br or I;
式（IV）中，1≤m≤20。In formula (IV), 1≤m≤20.
优选地，所述步骤c）为：Preferably, the step c) is:
将所述步骤b）得到的聚合物膜浸入含有交联剂的凝固浴中，进行交联反应，所述交联反应的温度为20℃～150℃，得到超滤膜或纳滤膜。The polymer membrane obtained in the step b) is immersed in a coagulation bath containing a crosslinking agent to carry out a crosslinking reaction. The temperature of the crosslinking reaction is 20° C. to 150° C. to obtain an ultrafiltration membrane or a nanofiltration membrane.
优选地，所述步骤c）为：Preferably, the step c) is:
c1）将所述步骤b）得到的聚合物膜固化，得到初生膜；c1) curing the polymer film obtained in step b) to obtain a nascent film;
c2）将所述步骤c1）得到的初生膜浸入含有交联剂的溶液中，进行交联反应，所述交联反应的温度为20℃～150℃，得到超滤膜或纳滤膜。c2) immersing the nascent membrane obtained in the step c1) into a solution containing a crosslinking agent to carry out a crosslinking reaction, the temperature of the crosslinking reaction is 20° C. to 150° C. to obtain an ultrafiltration membrane or a nanofiltration membrane.
本发明还提供一种超滤膜或纳滤膜，由上述技术方案所述制备方法制得，所述超滤膜或纳滤膜的厚度为5μm～500μm。The present invention also provides an ultrafiltration membrane or a nanofiltration membrane, which is prepared by the preparation method described in the above technical solution, and the thickness of the ultrafiltration membrane or nanofiltration membrane is 5 μm to 500 μm.
本发明提供了一种超滤膜或纳滤膜的制备方法，以具有式（I）或式（II）结构的聚合物为制膜原料，将其在交联剂的作用下进行交联反应，控制交联反应的温度为20℃～150℃，得到超滤膜或纳滤膜。本发明可以先将聚合物与交联剂进行交联反应，然后将交联后的聚合物进行制膜，得到超滤膜或纳滤膜；也可以先将聚合物进行制膜，再与交联剂进行交联反应，得到超滤膜或纳滤膜。本发明采用如式（I）或式（II）所示结构的化合物作为制膜原料，该聚合物中含有可交联的叔胺基团，在上述反应温度下，易与交联剂发生交联反应，得到网状结构的交联产物，在膜中同样形成网状的结构，使所得超滤膜或纳滤膜在酸性和碱性溶液中呈现不溶不融的现象。因此，本发明提供的方法制备的超滤膜或纳滤膜在酸性和碱性环境中具有良好的稳定性。另外，本发明提供的方法得到的超滤膜或纳滤膜具有较好的耐溶剂性。实验结果表明：本发明以主链含叔胺基团的聚芳醚砜为原料得到的超滤膜或纳滤膜，在摩尔浓度为0.5mol/L的HCl水溶液中浸泡前，膜的乙醇通量为292L/(m2·h)，对罗丹明6B的截留率为99.7%，而浸泡72h后，膜的乙醇通量为272L/(m2·h)，对罗丹明6B的截留率为99.8%；在摩尔浓度为0.5mol/L的NaOH水溶液中浸泡前，膜的乙醇通量为292L/(m2·h)，对罗丹明6B的截留率为99.7%，而浸泡72h后，膜的乙醇通量为279L/(m2·h)，对罗丹明6B的截留率为99.4%。The present invention provides a preparation method of ultrafiltration membrane or nanofiltration membrane. The polymer with the structure of formula (I) or formula (II) is used as the raw material for membrane production, and it is subjected to crosslinking reaction under the action of a crosslinking agent , the temperature of the cross-linking reaction is controlled to be 20° C. to 150° C. to obtain an ultrafiltration membrane or a nanofiltration membrane. In the present invention, the polymer and the cross-linking agent can be cross-linked first, and then the cross-linked polymer can be formed into a membrane to obtain an ultrafiltration membrane or a nanofiltration membrane; Linking agent for cross-linking reaction to obtain ultrafiltration membrane or nanofiltration membrane. The present invention uses the compound with the structure shown in formula (I) or formula (II) as the film-making raw material. The polymer contains cross-linkable tertiary amine groups, which are easy to cross-link with the cross-linking agent at the above reaction temperature. A cross-linked product with a network structure is obtained through a cross-linking reaction, which also forms a network structure in the membrane, making the obtained ultrafiltration membrane or nanofiltration membrane insoluble and insoluble in acidic and alkaline solutions. Therefore, the ultrafiltration membrane or nanofiltration membrane prepared by the method provided by the invention has good stability in acidic and alkaline environments. In addition, the ultrafiltration membrane or nanofiltration membrane obtained by the method provided by the invention has better solvent resistance. Experimental result shows: the ultrafiltration membrane or nanofiltration membrane that the present invention obtains with main chain containing the polyaryl ether sulfone of tertiary amino group as raw material, before the molar concentration is soaked in the HCl aqueous solution of 0.5mol/L, the ethanol of membrane passes through The ethanol flux of the membrane was 272L/(m2 h) , and the rejection rate of rhodamine 6B was 99.7%. 99.8%; before soaking in NaOH aqueous solution with a molar concentration of 0.5mol/L, the ethanol flux of the membrane was 292L/(m2 h), and the rejection rate of rhodamine 6B was 99.7%, and after soaking for 72h, the membrane The ethanol flux is 279L/(m2 ·h), and the rejection rate of rhodamine 6B is 99.4%.
具体实施方式Detailed ways
本发明提供了一种超滤膜或纳滤膜的制备方法，包括以下步骤：The invention provides a kind of preparation method of ultrafiltration membrane or nanofiltration membrane, comprises the following steps:
a）制备聚合物溶液，所述聚合物具有式（I）或式（II）所示结构：a) preparing a polymer solution, the polymer having a structure shown in formula (I) or formula (II):
其中，1≤x≤20；1≤y≤20；0≤z≤1；1≤n≤10000；Among them, 1≤x≤20; 1≤y≤20; 0≤z≤1; 1≤n≤10000;
其中，R1、R2、R3、R4、R5、R6、R7和R8至少有一个为-CH2-N(CH3)2；0≤z≤1；1≤n≤10000；Among them, at least one of R1 , R2 , R3 , R4 , R5 , R6 , R7 and R8 is -CH2 -N(CH3 )2 ; 0≤z≤1; 1≤n≤ 10000;
所述式（II）中Ar具有式(101)～式(105)所示结构中的任意一种：Ar in the formula (II) has any one of the structures shown in formula (101) to formula (105):
b）将所述步骤a）的聚合物溶液与交联剂混合，进行交联反应，得到制膜液，所述交联反应的温度为20℃～150℃；b) mixing the polymer solution in the step a) with a cross-linking agent to perform a cross-linking reaction to obtain a film-forming liquid, and the temperature of the cross-linking reaction is 20°C to 150°C;
c）将所述步骤b）制膜液进行制膜，得到超滤膜或纳滤膜。c) The membrane-forming solution in step b) is used to form a membrane to obtain an ultrafiltration membrane or a nanofiltration membrane.
本发明首先制备得到聚合物溶液；再将所述聚合物溶液与交联剂混合，进行交联反应，得到制膜液，所述交联反应的温度为20℃～150℃；最后将所述制膜液进行制膜，得到超滤膜或纳滤膜。本发明采用的聚合物含有叔胺基团，在上述反应温度下，易与交联剂发生交联反应，得到网状结构的交联产物，将交联产物制膜后，在膜中同样形成网状的结构，使所得到的纳滤膜或超滤膜在酸性和碱性溶液中呈现不溶不融的现象。因此，通过本发明提供的方法制备的超滤膜或纳滤膜在酸性和碱性环境中具有良好的稳定性。另外，本发明提供的方法得到的超滤膜或纳滤膜也具有较好的耐溶剂性。In the present invention, a polymer solution is first prepared; then the polymer solution is mixed with a cross-linking agent to perform a cross-linking reaction to obtain a film-forming liquid, and the temperature of the cross-linking reaction is 20°C to 150°C; finally, the The membrane-forming liquid is used for membrane-forming to obtain an ultrafiltration membrane or a nanofiltration membrane. The polymer used in the present invention contains tertiary amine groups. At the above reaction temperature, it is easy to undergo a cross-linking reaction with a cross-linking agent to obtain a cross-linked product with a network structure. After the cross-linked product is made into a film, it also forms a The network structure makes the obtained nanofiltration membrane or ultrafiltration membrane insoluble and insoluble in acidic and alkaline solutions. Therefore, the ultrafiltration membrane or nanofiltration membrane prepared by the method provided by the invention has good stability in acidic and alkaline environments. In addition, the ultrafiltration membrane or nanofiltration membrane obtained by the method provided by the invention also has better solvent resistance.
本发明制备得到聚合物溶液，所述聚合物为具有式（I）或式（II）所示结构的化合物，所述式（I）表示的为侧链具有叔胺基的聚芳醚砜，所述式（II）表示的为主链具有叔胺基的聚芳醚砜。在本发明中，所述式（I）中x的取值范围为1≤x≤20，优选的，2≤x≤15，更优选的，3≤x≤10；The present invention prepares a polymer solution, the polymer is a compound having a structure represented by formula (I) or formula (II), and the formula (I) represents a polyarylethersulfone having a tertiary amino group in the side chain, The formula (II) represents polyarylethersulfone having a tertiary amino group in the main chain. In the present invention, the value range of x in the formula (I) is 1≤x≤20, preferably, 2≤x≤15, more preferably, 3≤x≤10;
所述y的取值范围为1≤y≤20，优选的，2≤y≤15，更优选的，3≤y≤10；The value range of y is 1≤y≤20, preferably, 2≤y≤15, more preferably, 3≤y≤10;
所述z的取值范围为0≤z≤1，优选的，0.5≤z≤1，更优选的，z=1；The value range of z is 0≤z≤1, preferably, 0.5≤z≤1, more preferably, z=1;
所述n是聚合度，n的取值范围为1≤n≤10000，优选的，10≤n≤1000，更优选的，20≤n≤500，最优选的，50≤n≤200。The n is the degree of polymerization, and the value range of n is 1≤n≤10000, preferably, 10≤n≤1000, more preferably, 20≤n≤500, most preferably, 50≤n≤200.
当所述式（I）中x为3，z为1时，所述聚合物具有式（VI）所示结构：When x is 3 and z is 1 in the formula (I), the polymer has the structure shown in the formula (VI):
本发明对所述式（I）结构的聚合物的制备方法没有特殊的限制，采用本领域技术人员熟知侧链具有叔胺基的聚芳醚砜的制备方法即可。本发明优选采用申请号为200910259861.0的中国专利公开的方法制备。The present invention has no special limitation on the preparation method of the polymer with the structure of formula (I), and the preparation method of polyarylethersulfone having a tertiary amine group in the side chain that is well known to those skilled in the art can be used. The present invention is preferably prepared by the method disclosed in Chinese Patent Application No. 200910259861.0.
在本发明中，所述式（II）中，R1、R2、R3、R4、R5、R6、R7和R8至少有一个为-CH2-N(CH3)2，所述R1、R2、R3、R4、R5、R6、R7和R8中不为-CH2-N(CH3)2的基团优选为H；优选的R1、R2、R3和R4同时为-CH2-N(CH3)2，R5、R6、R7和R8同时为H；更优选的R1、R2、R3、R4、R5、R6、R7和R8同时为-CH2-N(CH3)2；In the present invention, in the formula (II), at least one of R1 , R2 , R3 , R4 , R5 , R6 , R7 and R8 is -CH2 -N(CH3 )2 , the group of R1 , R2 , R3 , R4 , R5 , R6 , R7 and R8 that is not -CH2 -N(CH3 )2 is preferably H; preferred R1 , R2 , R3 and R4 are -CH2 -N(CH3 )2 at the same time, R5 , R6 , R7 and R8 are H at the same time; more preferably R1 , R2 , R3 , R4 , R5 , R6 , R7 and R8 are -CH2 -N(CH3 )2 at the same time;
所述式（II）中，z的取值范围为0≤z≤1，优选的，0.5≤z≤1，更优选的z=1；In the formula (II), the value range of z is 0≤z≤1, preferably, 0.5≤z≤1, more preferably z=1;
所述n是聚合度，n的取值范围为1≤n≤10000，优选的，10≤n≤1000，更优选的，20≤n≤500，最优选的，50≤n≤200。The n is the degree of polymerization, and the value range of n is 1≤n≤10000, preferably, 10≤n≤1000, more preferably, 20≤n≤500, most preferably, 50≤n≤200.
在本发明中，所述式（II）中的Ar具有式(101)～式(105)所示结构中的任意一种，优选具有式（102）、式（103）或式（104）所示结构中的任意一种，更优选为具有式（102）所示结构。在本发明中，式（II）中与Ar相连的两个-O-在Ar取代基上优选呈对位取代，所述R1、R2、R3、R4、R5、R6、R7或R8可取代Ar上剩余的任意位置。In the present invention, Ar in the formula (II) has any one of the structures shown in the formula (101) to the formula (105), preferably has the structure represented by the formula (102), the formula (103) or the formula (104). Any one of the structures shown, more preferably having the structure shown in formula (102). In the present invention, the two -O- linked to Ar in formula (II) are preferably para-substituted on the Ar substituent, and the R1 , R2 , R3 , R4 , R5 , R6 , R7 or R8 can replace any remaining position on Ar.
在本发明中，当所述R1、R2、R3和R4同时为-CH2-N(CH3)2，z=1，Ar具有式（102）所示结构时，所述聚合物具有式（VII）所示结构：In the present invention, when the R1 , R2 , R3 and R4 are simultaneously -CH2 -N(CH3 )2 , z=1, and Ar has the structure shown in formula (102), the polymerization The substance has a structure shown in formula (VII):
本发明对所述式（II）结构的聚合物的制备方法没有特殊的限制，采用本领域技术人员熟知主链具有叔胺基的聚芳醚砜的制备方法即可。本发明优选采用申请号为200910259575.4的中国专利公开的方法制备。The present invention has no special limitation on the preparation method of the polymer with the structure of formula (II), and the preparation method of polyarylethersulfone having a tertiary amino group in the main chain well known to those skilled in the art can be used. The present invention is preferably prepared by the method disclosed in Chinese Patent Application No. 200910259575.4.
本发明对所述聚合物溶液中的溶剂没有特殊的限制，采用本领域技术人员熟知的能够溶解所述具有式（I）或式（II）结构聚合物的溶剂即可。在本发明中，所述溶剂优选为N,N-二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜和四氢呋喃中的一种或多种，更优选为N,N-二甲基甲酰胺和四氢呋喃中的一种或两种，最优选为N,N-二甲基甲酰胺。在本发明中，所述聚合物溶液的质量浓度优选为0.5%～50.0%，更优选为3.0%～30.0%，最优选为8.0%～20.0%。In the present invention, there is no special limitation on the solvent in the polymer solution, and a solvent known to those skilled in the art that can dissolve the polymer having the structure of formula (I) or formula (II) can be used. In the present invention, the solvent is preferably one or more of N,N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and tetrahydrofuran, more preferably One or both of N,N-dimethylformamide and tetrahydrofuran, most preferably N,N-dimethylformamide. In the present invention, the mass concentration of the polymer solution is preferably 0.5%-50.0%, more preferably 3.0%-30.0%, most preferably 8.0%-20.0%.
本发明对所述制备聚合物溶液的反应条件没有特殊限制，采用本领域技术人员熟知的制备聚合物溶液的技术方案即可。本发明优选将所述聚合物和溶剂混合，加热搅拌后，得到聚合物溶液。本发明对所述加热的方法没有特殊的限制，采用本领域技术人员熟知的加热的技术方案即可。在本发明中，所述加热的温度优选为40℃～150℃，更优选为50℃～100℃，最优选为55℃～80℃。本发明对所述搅拌方法没有特殊的限制，采用本领域技术人员熟知的搅拌的技术方案即可。在本发明中，所述搅拌的速度优选为10r/min～1000r/min，更优选为200r/min～900r/min，最优选为400r/min～800r/min。In the present invention, there is no special limitation on the reaction conditions for preparing the polymer solution, and the technical solution for preparing the polymer solution well known to those skilled in the art can be adopted. In the present invention, the polymer is preferably mixed with a solvent, and heated and stirred to obtain a polymer solution. The present invention has no special limitation on the heating method, and the heating technical solution well known to those skilled in the art can be adopted. In the present invention, the heating temperature is preferably 40°C to 150°C, more preferably 50°C to 100°C, and most preferably 55°C to 80°C. The present invention has no special limitation on the stirring method, and a stirring technical solution well known to those skilled in the art can be used. In the present invention, the stirring speed is preferably 10r/min-1000r/min, more preferably 200r/min-900r/min, most preferably 400r/min-800r/min.
得到聚合物溶液后，本发明将所述聚合物溶液与交联剂混合，进行交联反应，得到制膜液，所述交联反应的温度为20℃～150℃。本发明优选向所述聚合物溶液中加入交联剂，在20℃～150℃下进行交联反应。本发明采用的制膜聚合物结构中含有叔胺基团，在上述反应温度下，该聚合物能够与交联剂发生交联反应，得到网状结构的交联产物，将所述交联产物进行制膜后，在膜中同样形成网状的结构，使所得膜在酸性和碱性溶液中呈现不溶不融的现象，具有很好的耐酸性和耐碱性。另外，本发明提供的方法得到的超滤膜或纳滤膜也具有较好的耐溶剂性。After the polymer solution is obtained, the present invention mixes the polymer solution with a cross-linking agent to carry out a cross-linking reaction to obtain a membrane-forming liquid, and the temperature of the cross-linking reaction is 20° C. to 150° C. In the present invention, it is preferred to add a cross-linking agent to the polymer solution, and carry out the cross-linking reaction at 20°C to 150°C. The film-forming polymer structure adopted in the present invention contains tertiary amine groups, and at the above reaction temperature, the polymer can undergo a crosslinking reaction with a crosslinking agent to obtain a crosslinked product of a network structure, and the crosslinked product After the film is made, a network structure is also formed in the film, so that the obtained film is insoluble and infusible in acidic and alkaline solutions, and has good acid and alkali resistance. In addition, the ultrafiltration membrane or nanofiltration membrane obtained by the method provided by the invention also has better solvent resistance.
在本发明中，所述的交联剂优选为具有式（III）、式（IV）和式（V）所示结构的化合物中的一种或多种：In the present invention, the crosslinking agent is preferably one or more of the compounds having the structures shown in formula (III), formula (IV) and formula (V):
其中，X1、X2、X3、X4或X5独立地选自Cl、Br或I；Wherein, X1 , X2 , X3 , X4 or X5 are independently selected from Cl, Br or I;
式（IV）中，1≤m≤20；In formula (IV), 1≤m≤20;
所述交联剂更优选为对二氯苄、对二溴苄、1,2-二氯乙烷、1,2-二溴乙烷、1,4-二氯丁烷、1,4-二溴丁烷、1,6-二氯己烷、1,6-二溴己烷、1,3-环氧丙烷、1-氯-2,3-环氧丙烷和1-溴-2,3-环氧丙烷中的一种或多种，最优选为1,3-环氧丙烷和1,2-二溴乙烷中的一种或两种。在本发明中，所述交联剂与所述聚合物的质量比优选为0.0001～0.1:1，更优选为0.001～0.08:1，最优选为0.01～0.06:1。在本发明中，所述交联反应的时间优选为10min～300min，更优选为30min～250min，最优选为40min～150min，最最优选为50min～100min；所述交联反应的温度为20℃～150℃，优选为30℃～120℃，更优选为40℃～110℃，最优选为50℃～100℃。The crosslinking agent is more preferably p-dichlorobenzyl, p-dibromobenzyl, 1,2-dichloroethane, 1,2-dibromoethane, 1,4-dichlorobutane, 1,4-dichlorobenzyl Bromobutane, 1,6-dichlorohexane, 1,6-dibromohexane, 1,3-propylene oxide, 1-chloro-2,3-propylene oxide and 1-bromo-2,3- One or more of propylene oxide, most preferably one or both of 1,3-propylene oxide and 1,2-dibromoethane. In the present invention, the mass ratio of the crosslinking agent to the polymer is preferably 0.0001-0.1:1, more preferably 0.001-0.08:1, most preferably 0.01-0.06:1. In the present invention, the time of the crosslinking reaction is preferably 10min to 300min, more preferably 30min to 250min, most preferably 40min to 150min, most preferably 50min to 100min; the temperature of the crosslinking reaction is 20°C ~150°C, preferably 30°C to 120°C, more preferably 40°C to 110°C, most preferably 50°C to 100°C.
本发明在20℃～150℃下，将具有式（I）或式（II）所示结构的聚合物与交联剂反应，再将得到的交联反应产物制膜，得到超滤膜或纳滤膜。本发明采用的聚合物结构中含有叔胺基，在上述反应温度下，能够与交联剂进行交联反应，提高了得到的超滤膜或纳滤膜的耐酸碱性和耐溶剂性。以式（VI）所示结构的聚合物为例，所述聚合物与交联剂进行交联反应得到如式（VIII）所示结构的交联反应产物：In the present invention, at 20°C to 150°C, the polymer having the structure represented by formula (I) or formula (II) is reacted with a crosslinking agent, and then the obtained crosslinking reaction product is formed into a membrane to obtain an ultrafiltration membrane or a nanofiltration membrane. filter membrane. The polymer structure adopted in the present invention contains tertiary amine groups, and can carry out crosslinking reaction with a crosslinking agent at the above reaction temperature, thereby improving the acid and alkali resistance and solvent resistance of the obtained ultrafiltration membrane or nanofiltration membrane. Taking the polymer with the structure shown in formula (VI) as an example, the polymer undergoes a cross-linking reaction with a cross-linking agent to obtain a cross-linked reaction product with the structure shown in formula (VIII):
其中，Crosslinking agent表示交联剂。Wherein, Crosslinking agent represents a crosslinking agent.
得到制膜液后，本发明将所述制膜液进行制膜，得到超滤膜或纳滤膜。本发明对所述制膜的过程没有特殊的限制，采用本领域技术人员熟知的制膜技术方案即可。在本发明中，所述制膜的过程优选为：After the membrane-forming solution is obtained, the present invention uses the membrane-forming solution to form a membrane to obtain an ultrafiltration membrane or a nanofiltration membrane. The present invention has no special limitation on the film-making process, and the film-making technical solution well known to those skilled in the art can be adopted. In the present invention, the process of making the film is preferably:
将所述制膜液进行过滤、脱泡、刮膜，得到超滤膜或纳滤膜前体；Filtrating, defoaming, and scraping the membrane-forming solution to obtain an ultrafiltration membrane or nanofiltration membrane precursor;
将所述超滤膜或纳滤膜前体在空气中静置、固化，得到超滤膜或纳滤膜。The ultrafiltration membrane or nanofiltration membrane precursor is left to stand and solidified in the air to obtain an ultrafiltration membrane or nanofiltration membrane.
本发明对所述过滤和脱泡的方法没有特殊的限制，采用本领域技术人员熟知的制膜过程中的过滤和脱泡技术方案即可。本发明对所述刮膜没有特殊的限制，优选采用本领域技术人员熟知刮膜机进行刮膜即可；在本发明中，所述刮膜中刮刀高度优选为10μm～1000μm，更优选为50μm～800μm，最优选为100μm～600μm，最最优选为150μm～400μm。The present invention has no special limitation on the filtering and defoaming methods, and the technical scheme of filtering and defoaming in the membrane-making process well known to those skilled in the art can be adopted. The present invention has no special restrictions on the scraping film, and it is preferable to use a scraping machine well-known to those skilled in the art to scrape the film; in the present invention, the height of the scraper in the scraping film is preferably 10 μm to 1000 μm, more preferably 50 μm ~800 μm, most preferably 100 μm to 600 μm, most preferably 150 μm to 400 μm.
本发明在完成刮膜后，优选将得到的超滤膜或纳滤膜前体在空气中静置，所述静置时间优选为5s～300s，更优选为10s～200s，最优选为15s～60s。In the present invention, after the film scraping is completed, the obtained ultrafiltration membrane or nanofiltration membrane precursor is preferably left standing in the air, and the standing time is preferably 5s～300s, more preferably 10s～200s, most preferably 15s～ 60s.
本发明将所得超滤膜或纳滤膜前体静置后，将所述的超滤膜或纳滤膜前体进行固化。在本发明中，所述固化优选采用凝固浴或经热处理进行固化。本发明对所述凝固浴的组成没有特殊的限制，采用本领域技术人员熟知的制膜过程中采用的凝固浴即可；在本发明中，所述凝固浴优选包括水、盐水、乙醇、丙酮和醋酸中的一种或几种，更优选为水、盐水和醋酸中的一种或几种，最优选为水。在本发明中，所述热处理的温度优选为20℃～180℃，更优选为50℃～150℃，最优选为80℃～110℃；所述固化的时间优选为30min～2000min，更优选为300min～1800min，最优选为700min～1600min，最最优选为1000min～1500min。In the present invention, after the obtained ultrafiltration membrane or nanofiltration membrane precursor is left to stand, the ultrafiltration membrane or nanofiltration membrane precursor is solidified. In the present invention, the curing is preferably carried out by using a coagulation bath or by heat treatment. The present invention has no special limitation on the composition of the coagulation bath, and the coagulation bath used in the film-making process well known to those skilled in the art can be used; in the present invention, the coagulation bath preferably includes water, brine, ethanol, acetone and one or more of acetic acid, more preferably one or more of water, brine and acetic acid, most preferably water. In the present invention, the heat treatment temperature is preferably 20°C to 180°C, more preferably 50°C to 150°C, most preferably 80°C to 110°C; the curing time is preferably 30min to 2000min, more preferably 300min to 1800min, most preferably 700min to 1600min, most preferably 1000min to 1500min.
本发明在完成膜的固化后，优选将得到的超滤膜或纳滤膜再次与交联剂混合，进行交联反应。本发明优选将得到的超滤膜或纳滤膜浸入所述交联剂的溶液中，进行交联反应。本发明优选采用上述技术方案所述的交联剂，这里不再赘述。在本发明中，所述交联剂溶液的质量浓度优选为0.01%～100%，更优选为5%～50%，最优选为10%～30%；所述交联反应的温度优选为20℃～150℃，更优选为30℃～120℃，最优选为40℃～110℃；所述交联反应的时间优选为5min～1200min，更优选为30min～1000min，最优选为40min～500min，最最优选为50min～100min。In the present invention, after the curing of the membrane is completed, the obtained ultrafiltration membrane or nanofiltration membrane is preferably mixed with a crosslinking agent again to carry out a crosslinking reaction. In the present invention, the obtained ultrafiltration membrane or nanofiltration membrane is preferably immersed in the solution of the crosslinking agent to carry out the crosslinking reaction. The present invention preferably adopts the cross-linking agent described in the above technical solution, which will not be repeated here. In the present invention, the mass concentration of the crosslinking agent solution is preferably 0.01% to 100%, more preferably 5% to 50%, most preferably 10% to 30%; the temperature of the crosslinking reaction is preferably 20 °C to 150 °C, more preferably 30 °C to 120 °C, most preferably 40 °C to 110 °C; the time for the crosslinking reaction is preferably 5 min to 1200 min, more preferably 30 min to 1000 min, most preferably 40 min to 500 min, Most preferably, it is 50 min to 100 min.
本发明优选将得到的超滤膜或纳滤膜进行后处理。本发明对所述后处理没有特殊的限制，采用本领域技术人员熟知的制膜过程的后处理即可。本发明优选为采用水或醇类化合物对得到的超滤膜或纳滤膜进行清洗。在本发明中，所述醇类化合物优选为乙醇。In the present invention, the obtained ultrafiltration membrane or nanofiltration membrane is preferably post-treated. The present invention has no special limitation on the post-treatment, and the post-treatment of the film-forming process well-known to those skilled in the art can be used. The present invention preferably uses water or alcohol compounds to clean the obtained ultrafiltration membrane or nanofiltration membrane. In the present invention, the alcohol compound is preferably ethanol.
本发明还提供了一种超滤膜或纳滤膜的制备方法，包括以下步骤：The present invention also provides a kind of preparation method of ultrafiltration membrane or nanofiltration membrane, comprises the following steps:
a）制备聚合物溶液，所述聚合物具有式（I）或式（II）所示结构：a) preparing a polymer solution, the polymer having a structure shown in formula (I) or formula (II):
其中，1≤x≤20；1≤y≤20；0≤z≤1；1≤n≤10000；Among them, 1≤x≤20; 1≤y≤20; 0≤z≤1; 1≤n≤10000;
其中，R1、R2、R3、R4、R5、R6、R7和R8至少有一个为-CH2-N(CH3)2；0≤z≤1；1≤n≤10000；Among them, at least one of R1 , R2 , R3 , R4 , R5 , R6 , R7 and R8 is -CH2 -N(CH3 )2 ; 0≤z≤1; 1≤n≤ 10000;
所述式（II）中Ar具有式(101)～式(105)所示结构中的任意一种：Ar in the formula (II) has any one of the structures shown in formula (101) to formula (105):
b）将所述步骤a）的聚合物溶液进行制膜，得到聚合物膜；b) forming a film from the polymer solution in step a) to obtain a polymer film;
c）将所述步骤b）得到的聚合物膜与交联剂混合，进行交联反应，所述交联反应的温度为20℃～150℃，得到超滤膜或纳滤膜。c) mixing the polymer membrane obtained in the step b) with a cross-linking agent to perform a cross-linking reaction, the temperature of the cross-linking reaction being 20° C. to 150° C. to obtain an ultrafiltration membrane or a nanofiltration membrane.
本发明首先制备得到聚合物溶液；将所述聚合物溶液进行制膜，得到聚合物膜；再将聚合物膜与交联剂混合，进行交联反应，所述交联反应的温度为20℃～150℃，得到超滤膜或纳滤膜。本发明采用如式（I）或式（II）所示结构的化合物作为制膜聚合物，所述聚合物含有叔胺基团，在上述温度下，将所述聚合物制成聚合物膜，聚合物膜再与交联剂发生交联反应，在膜中形成网状的结构，使所得膜在酸性或碱性溶液中呈现不溶不融的现象。因此，通过本发明提供的方法制备的超滤膜或纳滤膜在酸性和碱性环境中具有良好的稳定性。另外，本发明提供的方法得到的超滤膜或纳滤膜也具有较好的耐溶剂性。In the present invention, a polymer solution is first prepared; the polymer solution is formed into a film to obtain a polymer film; then the polymer film is mixed with a cross-linking agent to perform a cross-linking reaction, and the temperature of the cross-linking reaction is 20°C ~150°C to obtain ultrafiltration membrane or nanofiltration membrane. The present invention adopts the compound with the structure shown in formula (I) or formula (II) as the film-forming polymer, and the polymer contains tertiary amine groups. At the above temperature, the polymer is made into a polymer film, The polymer film reacts with the cross-linking agent to form a network structure in the film, so that the obtained film is insoluble and infusible in acidic or alkaline solution. Therefore, the ultrafiltration membrane or nanofiltration membrane prepared by the method provided by the invention has good stability in acidic and alkaline environments. In addition, the ultrafiltration membrane or nanofiltration membrane obtained by the method provided by the invention also has better solvent resistance.
本发明制备得到聚合物溶液，本发明优选采用上述技术方案所述聚合物溶液的制备方法制备得到聚合物溶液，在此不再赘述。The polymer solution is prepared in the present invention, and the polymer solution is preferably prepared by the method for preparing the polymer solution described in the above technical solution in the present invention, which will not be repeated here.
得到聚合物溶液后，本发明将所述聚合物溶液进行制膜，得到聚合物膜。本发明对所述制膜的过程没有特殊的限制，采用本领域技术人员熟知的制膜技术方案即可。本发明优选将所述聚合物溶液进行过滤、脱泡、刮膜，得到聚合物膜。本发明对所述过滤和脱泡的方法没有特殊的限制，采用本领域技术人员熟知的制膜过程中的过滤和脱泡技术方案即可。本发明对所述刮膜没有特殊的限制，优选采用本领域技术人员熟知刮膜机进行刮膜即可；在本发明中，所述刮膜中刮刀高度优选为10μm～1000μm，更优选为50μm～800μm，最优选为100μm～600μm，最最优选为150μm～400μm。After obtaining the polymer solution, the present invention forms the polymer solution into a film to obtain a polymer film. The present invention has no special limitation on the film-making process, and the film-making technical solution well known to those skilled in the art can be adopted. In the present invention, the polymer solution is preferably filtered, defoamed, and film scraped to obtain a polymer film. The present invention has no special limitation on the filtering and defoaming methods, and the technical scheme of filtering and defoaming in the membrane-making process well known to those skilled in the art can be adopted. The present invention has no special restrictions on the scraping film, and it is preferable to use a scraping machine well-known to those skilled in the art to scrape the film; in the present invention, the height of the scraper in the scraping film is preferably 10 μm to 1000 μm, more preferably 50 μm ~800 μm, most preferably 100 μm to 600 μm, most preferably 150 μm to 400 μm.
在完成所述刮膜后，本发明优选将得到的膜在空气中静置，得到聚合物膜。在本发明中，所述静置时间优选为5s～300s，更优选为10s～200s，最优选为15s～60s。After the scraping film is completed, the present invention preferably leaves the obtained film in air to obtain a polymer film. In the present invention, the standing time is preferably 5s-300s, more preferably 10s-200s, most preferably 15s-60s.
得到聚合物膜后，本发明将所述聚合物膜与交联剂混合，进行交联反应，所述交联反应的温度为20℃～150℃，得到超滤膜或纳滤膜。After the polymer film is obtained, the present invention mixes the polymer film with a cross-linking agent to carry out a cross-linking reaction. The temperature of the cross-linking reaction is 20° C. to 150° C. to obtain an ultrafiltration membrane or a nanofiltration membrane.
在本发明中，所述聚合物膜与交联剂的交联反应可以为：In the present invention, the crosslinking reaction of the polymer film and the crosslinking agent can be:
将上述技术方案得到的聚合物膜浸入含有交联剂的凝固浴中，进行交联反应，所述交联反应的温度为20℃～150℃，得到超滤膜或纳滤膜。The polymer membrane obtained by the above technical solution is immersed in a coagulation bath containing a crosslinking agent to carry out a crosslinking reaction, the temperature of the crosslinking reaction is 20° C. to 150° C. to obtain an ultrafiltration membrane or a nanofiltration membrane.
本发明优选采用上述技术方案所述的交联剂，在此不再赘述。在本发明中，所述交联剂与聚合物的质量比优选为0.0001～0.1:1，更优选为0.001～0.08:1，最优选为0.01～0.06:1；所述交联反应时间优选为5min～300min，更优选为30min～200min，最优选为40min～150min，最最优选为50min～100min。所述交联反应的温度为20℃～150℃，优选为30℃～120℃，更优选为40℃～110℃，最优选为50℃～100℃。本发明优选采用上述技术方案所述凝固浴对聚合物膜进行固化，在此不再赘述。在本发明中，所述凝固浴中交联剂的质量浓度优选为0.5%～100%，更优选为5%～50%，最优选为10%～30%。The present invention preferably adopts the cross-linking agent described in the above technical solution, which will not be repeated here. In the present invention, the mass ratio of the cross-linking agent to the polymer is preferably 0.0001-0.1:1, more preferably 0.001-0.08:1, most preferably 0.01-0.06:1; the cross-linking reaction time is preferably 5 min to 300 min, more preferably 30 min to 200 min, most preferably 40 min to 150 min, most preferably 50 min to 100 min. The temperature of the crosslinking reaction is 20°C-150°C, preferably 30°C-120°C, more preferably 40°C-110°C, most preferably 50°C-100°C. In the present invention, the coagulation bath described in the above technical solution is preferably used to solidify the polymer film, which will not be repeated here. In the present invention, the mass concentration of the crosslinking agent in the coagulation bath is preferably 0.5%-100%, more preferably 5%-50%, and most preferably 10%-30%.
在本发明中，所述聚合物膜与交联剂的交联反应还可以为：In the present invention, the crosslinking reaction of the polymer film and the crosslinking agent can also be:
将上述技术方案得到的聚合物膜固化，得到初生膜；The polymer film obtained by the above technical scheme is solidified to obtain a nascent film;
将所述初生膜浸入含有交联剂的溶液中，进行交联反应，所述交联反应的温度为20℃～150℃，得到超滤膜或纳滤膜。The nascent membrane is immersed in a solution containing a cross-linking agent to carry out a cross-linking reaction. The temperature of the cross-linking reaction is 20° C. to 150° C. to obtain an ultrafiltration membrane or a nanofiltration membrane.
本发明将上述技术方案得到的聚合物膜固化，得到初生膜。本发明优选将所述聚合物膜浸入凝固浴中或经热处理进行固化。本发明优选采用上述技术方案所述凝固浴对聚合物膜进行固化，在此不再赘述。在本发明中，所述热处理温度优选为20℃～180℃，更优选为50℃～150℃，最优选为80℃～110℃。在本发明中，所述固化时间优选为30min～2000min，更优选为300min～1800min，最优选为700min～1600min，最最优选为1000min～1500min；The present invention solidifies the polymer film obtained by the above technical scheme to obtain a nascent film. In the present invention, the polymer film is preferably cured by immersing it in a coagulation bath or by heat treatment. In the present invention, the coagulation bath described in the above technical solution is preferably used to solidify the polymer film, which will not be repeated here. In the present invention, the heat treatment temperature is preferably 20°C to 180°C, more preferably 50°C to 150°C, and most preferably 80°C to 110°C. In the present invention, the curing time is preferably 30 min to 2000 min, more preferably 300 min to 1800 min, most preferably 700 min to 1600 min, most preferably 1000 min to 1500 min;
得到初生膜后，本发明将所述初生膜浸入含有交联剂的溶液中，进行交联反应，所述交联反应的温度为20℃～150℃，得到超滤膜或纳滤膜。本发明优选采用上述技术方案所述的交联剂，在此不再赘述。在本发明中，所述交联反应时间优选为5min～1200min，更优选为30min～1000min，最优选为40min～500min，最最优选为50min～100min；所述交联反应的温度优选为20℃～150℃，更优选为30℃～120℃，最优选为40℃～110℃。在本发明中，所述交联剂溶液的质量浓度优选为0.01%～100%，更优选为5%～50%，最优选为10%～30%。After the nascent membrane is obtained, the present invention immerses the nascent membrane into a solution containing a crosslinking agent to perform a crosslinking reaction. The temperature of the crosslinking reaction is 20° C. to 150° C. to obtain an ultrafiltration membrane or a nanofiltration membrane. The present invention preferably adopts the cross-linking agent described in the above technical solution, which will not be repeated here. In the present invention, the time for the crosslinking reaction is preferably 5min to 1200min, more preferably 30min to 1000min, most preferably 40min to 500min, most preferably 50min to 100min; the temperature of the crosslinking reaction is preferably 20°C ~150°C, more preferably 30°C to 120°C, most preferably 40°C to 110°C. In the present invention, the mass concentration of the crosslinking agent solution is preferably 0.01%-100%, more preferably 5%-50%, and most preferably 10%-30%.
本发明优选将得到的超滤膜或纳滤膜进行后处理。本发明对所述后处理没有特殊的限制，采用本领域技术人员熟知的制膜过程的后处理即可。本发明优选为采用水或醇类化合物对得到的超滤膜或纳滤膜进行清洗。在本发明中，所述醇类化合物优选为乙醇。In the present invention, the obtained ultrafiltration membrane or nanofiltration membrane is preferably post-treated. The present invention has no special limitation on the post-treatment, and the post-treatment of the film-forming process well-known to those skilled in the art can be used. The present invention preferably uses water or alcohol compounds to clean the obtained ultrafiltration membrane or nanofiltration membrane. In the present invention, the alcohol compound is preferably ethanol.
本发明提供了一种超滤膜或纳滤膜，由上述技术方案所述方法制备得到，所述超滤膜或纳滤膜厚度为5μm～500μm，优选为20μm～400μm，更优选为30μm～300μm，最优选为40μm～200μm，最最优选为50μm～100μm。本发明提供的方法制备得到的超滤膜或纳滤膜的乙醇通量为200L/(m2·h)～300L/(m2·h)，对罗丹明6B的截留率达到99%以上。The present invention provides an ultrafiltration membrane or a nanofiltration membrane, which is prepared by the method described in the above technical solution. The thickness of the ultrafiltration membrane or nanofiltration membrane is 5 μm to 500 μm, preferably 20 μm to 400 μm, more preferably 30 μm to 300 μm, most preferably 40 μm to 200 μm, most preferably 50 μm to 100 μm. The ethanol flux of the ultrafiltration membrane or nanofiltration membrane prepared by the method provided by the invention is 200L/(m2 ·h)～300L/(m2 ·h), and the rejection rate of rhodamine 6B reaches more than 99%.
本发明对所制得的超滤膜或纳滤膜进行膜通量、膜截留率、耐酸性、耐碱性和耐溶剂性的性能测试，具体过程如下：The present invention carries out the performance test of membrane flux, membrane rejection, acid resistance, alkali resistance and solvent resistance to the prepared ultrafiltration membrane or nanofiltration membrane, and the specific process is as follows:
本发明中所述膜通量测试过程为：在25℃下，对有效膜面积为20.4cm2的超滤膜或纳滤膜进行测试，采用乙醇或水为测试液，将膜片在0.5MPa下预压120min，然后将压力降到0.2MPa，稳定30min后，根据公式(1)测定其通量：The membrane flux test process in the present invention is: at 25°C, the ultrafiltration membrane or nanofiltration membrane with an effective membrane area of20.4cm is tested, using ethanol or water as the test solution, and the membrane is tested at 0.5MPa Lower the pre-compression for 120 minutes, then reduce the pressure to 0.2MPa, and after 30 minutes of stabilization, measure the flux according to the formula (1):
其中，F为膜通量，单位为L/(m2·h)；Among them, F is the membrane flux, the unit is L/(m2 ·h);
V为透过液的体积，单位为mL;V is the volume of permeate, in mL;
A为有效膜面积，单位为cm2;A is the effective membrane area, the unit is cm2 ;
t为测试时间，单位为h。t is the test time, the unit is h.
本发明中所述膜截留率测试过程为：向乙醇测试液中加入浓度为200ppm的罗丹明6B，在0.4MPa下，运行30min后，收集滤液，用可见紫外分光光度计分别测定滤液和母液的吸光度，由吸光度推算出滤液和母液中罗丹明6B的浓度，利用公式（2）计算得到膜截留率：The membrane rejection testing process described in the present invention is: add the rhodamine 6B that concentration is 200ppm in the ethanol test solution, under 0.4MPa, after running 30min, collect filtrate, measure filtrate and mother liquor respectively with visible ultraviolet spectrophotometer Absorbance, calculate the concentration of rhodamine 6B in the filtrate and mother liquor from the absorbance, and use the formula (2) to calculate the membrane rejection rate:
其中，R为膜截留率，单位为%；Among them, R is the membrane rejection rate, the unit is %;
Cp为滤液中溶质质量浓度，单位为mg/L;Cp is the solute mass concentration in the filtrate, in mg/L;
Cf为母液中溶质质量浓度，单位为mg/L。Cf is the mass concentration of the solute in the mother liquor, in mg/L.
本发明中所述耐酸性测试过程为：截取一定面积的超滤膜或纳滤膜膜片，将其分别浸泡于摩尔浓度为0.5mol/L的HCl水溶液中6h、12h、18h、24h和72h，将膜片取出经充分水洗后，按照上述技术方案所述的方法测定膜的通量和截留率，对比浸泡前后膜性能的变化。The acid resistance test process described in the present invention is: cut off a certain area of ultrafiltration membrane or nanofiltration membrane diaphragm, soak it respectively in the HCl aqueous solution whose molar concentration is 0.5mol/L for 6h, 12h, 18h, 24h and 72h , After taking out the membrane and fully washing it with water, measure the flux and rejection rate of the membrane according to the method described in the above technical scheme, and compare the changes in membrane performance before and after soaking.
本发明中所述耐碱性测试过程为：截取一定面积的超滤膜或纳滤膜膜片，将其分别浸泡于摩尔浓度为0.5mol/L的NaOH水溶液中6h、12h、18h、24h和72h，将膜片取出经充分水洗后，按照上述技术方案所述的方法测定膜的通量和截留率，对比浸泡前后膜性能的变化。The alkali resistance test process described in the present invention is: cut off a certain area of ultrafiltration membrane or nanofiltration membrane diaphragm, soak it in the NaOH aqueous solution that molar concentration is 0.5mol/L respectively for 6h, 12h, 18h, 24h and After 72 hours, the membrane was taken out and fully washed with water, and the flux and rejection rate of the membrane were measured according to the method described in the above technical scheme, and the changes in membrane performance before and after immersion were compared.
本发明中所述耐溶剂测试过程为：截取一定面积的超滤膜或纳滤膜膜片，将其分别浸泡于乙醇、甲醇、丙酮、氯仿和N,N-二甲基甲酰胺中12h，将膜片取出经乙醇充分清洗后，按照上述技术方案所述的方法，测定膜的通量和截留率。The solvent resistance test process described in the present invention is: cut off a certain area of ultrafiltration membrane or nanofiltration membrane membrane, soak it in ethanol, methanol, acetone, chloroform and N,N-dimethylformamide for 12 hours respectively, After the diaphragm is taken out and fully cleaned with ethanol, the flux and rejection rate of the membrane are measured according to the method described in the above technical scheme.
结果表明，本发明提供的方法得到的超滤膜或纳滤膜的乙醇通量为200L/(m2·h)～300L/(m2·h)，对罗丹明6B的截留率达到99%以上，在酸性和碱性环境中具有良好的稳定性。另外，本发明提供的方法得到的超滤膜或纳滤膜也具有较好的耐溶剂性。The results show that the ethanol flux of the ultrafiltration membrane or nanofiltration membrane obtained by the method provided by the invention is 200L/(m2 h)～300L/(m2 h), and the retention rate of rhodamine 6B reaches 99%. Above, it has good stability in acidic and alkaline environments. In addition, the ultrafiltration membrane or nanofiltration membrane obtained by the method provided by the invention also has better solvent resistance.
本发明提供了一种超滤膜或纳滤膜的制备方法，以具有式（I）或式（II）结构的聚合物为制膜原料，将其在交联剂的作用下进行交联反应，控制交联反应的温度为20℃～150℃，得到超滤膜或纳滤膜。本发明可以先将聚合物与交联剂进行交联反应，然后将交联后的聚合物进行制膜，得到超滤膜或纳滤膜；也可以先将聚合物进行制膜，再与交联剂进行交联反应，得到超滤膜或纳滤膜。本发明采用如式（I）或式（II）所示结构的化合物作为制膜聚合物，该聚合物中含有可交联的叔胺基团，在20℃～150℃下，易与交联剂发生交联反应，得到网状结构的交联产物，在膜中同样形成网状的结构，使所得超滤膜或纳滤膜在酸性或碱性溶液中呈现不溶不融的现象。因此，通过本发明提供的方法制备的超滤膜或纳滤膜在酸性和碱性环境中具有良好的稳定性。另外，本发明提供的方法制备得到的超滤膜或纳滤膜也具有较好的耐溶剂性。The present invention provides a preparation method of ultrafiltration membrane or nanofiltration membrane. The polymer with the structure of formula (I) or formula (II) is used as the raw material for membrane production, and it is subjected to crosslinking reaction under the action of a crosslinking agent , the temperature of the cross-linking reaction is controlled to be 20° C. to 150° C. to obtain an ultrafiltration membrane or a nanofiltration membrane. In the present invention, the polymer and the cross-linking agent can be cross-linked first, and then the cross-linked polymer can be formed into a membrane to obtain an ultrafiltration membrane or a nanofiltration membrane; Linking agent for cross-linking reaction to obtain ultrafiltration membrane or nanofiltration membrane. The present invention adopts the compound with the structure shown in formula (I) or formula (II) as the film-forming polymer. A cross-linking reaction occurs with the agent to obtain a cross-linked product with a network structure, which also forms a network structure in the membrane, making the obtained ultrafiltration membrane or nanofiltration membrane insoluble in acidic or alkaline solution. Therefore, the ultrafiltration membrane or nanofiltration membrane prepared by the method provided by the invention has good stability in acidic and alkaline environments. In addition, the ultrafiltration membrane or nanofiltration membrane prepared by the method provided by the invention also has better solvent resistance.
为了进一步说明本发明，下面结合实施例对本发明提供的一种超滤膜或纳滤膜及其制备方法进行详细地描述，但不能将它们理解为对本发明保护范围的限定。In order to further illustrate the present invention, a kind of ultrafiltration membrane or nanofiltration membrane provided by the present invention and its preparation method are described in detail below in conjunction with the examples, but they should not be interpreted as limiting the protection scope of the present invention.
比较例1Comparative example 1
将100g聚砜（PSF）溶解于900g N,N-二甲基甲酰胺中，所述聚砜具有式（IX）所示结构，在60℃下加热搅拌溶解，搅拌速度为800r/min，得到质量浓度为10.00%的聚合物溶液；将聚合物溶液过滤、脱泡后在刮膜机上刮膜，控制刮刀高度为200μm，得到聚合物膜；将得到的聚合物膜在空气中静置20s后，浸入水中固化24h，制得超滤膜或纳滤膜。Dissolve 100g of polysulfone (PSF) in 900g of N,N-dimethylformamide, the polysulfone has the structure shown in formula (IX), heat and stir at 60°C to dissolve, and the stirring speed is 800r/min, to obtain A polymer solution with a mass concentration of 10.00%; after filtering the polymer solution and defoaming, scrape the film on a film scraper, and control the height of the scraper to 200 μm to obtain a polymer film; place the obtained polymer film in the air for 20 seconds , Soaked in water for 24 hours to solidify, to prepare ultrafiltration membrane or nanofiltration membrane.
本发明检测得到本发明比较例1所制得的膜厚度为80μm。The present invention detects that the thickness of the film prepared in Comparative Example 1 of the present invention is 80 μm.
本发明将所制得的膜进行膜通量测试，采用水作为测试液，按照上述技术方案所述的膜通量的测试方法，测试得到本发明比较例1制备的膜的水通量为529L/(m2·h)。In the present invention, the prepared membrane is tested for membrane flux, water is used as the test liquid, and according to the membrane flux test method described in the above technical scheme, the water flux of the membrane prepared in Comparative Example 1 of the present invention is tested to be 529L. /(m2 ·h).
本发明按照上述技术方案所述的膜截留率的测试方法，测试得到本发明比较例制备的膜对罗丹明6B的截留率为13.2%。According to the test method of the membrane rejection rate described in the above-mentioned technical scheme, the present invention obtains that the membrane rejection rate of rhodamine 6B prepared by the comparative example of the present invention is 13.2%.
本发明按照上述技术方案所述的耐酸性的测试方法，测试结果如表1所示，表1为本发明比较例1得到的膜的耐酸性测试结果。The present invention follows the test method for acid resistance described in the technical solution above, and the test results are shown in Table 1. Table 1 is the test result of the acid resistance of the film obtained in Comparative Example 1 of the present invention.
表1本发明比较例1得到的膜的耐酸性测试结果The acid resistance test result of the membrane that table 1 comparative example 1 of the present invention obtains
由表1可以看出，本发明比较例1得到的膜在HCl溶液中浸泡72h后，所得膜的通量为552L/(m2·h)，膜对罗丹明6B的截留率为13.1%。It can be seen from Table 1 that after the membrane obtained in Comparative Example 1 of the present invention was soaked in HCl solution for 72 hours, the flux of the obtained membrane was 552 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 13.1%.
本发明按照上述技术方案所述的耐碱性的测试方法，测试结果如表2所示，表2为本发明比较例1得到的膜的耐碱性测试结果。The present invention follows the test method for alkali resistance described in the technical solution above, and the test results are shown in Table 2, and Table 2 is the test result of the alkali resistance of the film obtained in Comparative Example 1 of the present invention.
表2本发明比较例1得到的膜的耐碱性测试结果The alkali resistance test result of the membrane that table 2 comparative example 1 of the present invention obtains
由表2可以看出，本发明比较例1得到的膜在NaOH碱性溶液中浸泡72h后，膜的通量为565L/(m2·h)，膜对罗丹明6B的截留率为13.6%。As can be seen from Table 2, after the membrane obtained in Comparative Example 1 of the present invention was soaked in NaOH alkaline solution for 72h, the flux of the membrane was565L /(m h), and the rejection rate of the membrane to Rhodamine 6B was 13.6%. .
本发明按照上述技术方案所述的耐溶剂性的测试方法，测试结果如表3所示，表3为本发明比较例1得到的膜的耐溶剂性测试结果。The present invention follows the test method for solvent resistance described in the technical solution above, and the test results are shown in Table 3, and Table 3 is the test result of the solvent resistance of the film obtained in Comparative Example 1 of the present invention.
表3本发明比较例1得到的膜的耐溶剂性测试结果The solvent resistance test result of the film that table 3 comparative example 1 of the present invention obtains
——：表示膜已经溶解——: Indicates that the film has been dissolved
由表3可以看出，本发明比较例1得到的膜在氯仿和N,N-二甲基甲酰胺中溶解。It can be seen from Table 3 that the membrane obtained in Comparative Example 1 of the present invention was dissolved in chloroform and N,N-dimethylformamide.
实施例1Example 1
在装有机械搅拌、冷凝器和分水器的三颈瓶中加入0.1mol N,N-二甲氨基丙胺；向三颈瓶中通入氨气，并将其缓慢升温至120℃，使三颈瓶中物料发生反应，生成N-二甲氨基丙基-3,3′-双（4-羟基苯基）苯并吡咯酮（PPH-TA）；在装有机械搅拌、冷凝器和分水器的三颈瓶中加入0.1molPPH-TA，0.1mol4,4′-二氯二苯砜，0.2mol无水碳酸钾、138mL二甲亚砜、70mL甲苯；向三颈瓶中通入氮气，并将三颈瓶逐渐升温至150℃，使甲苯回流，回流4h后，逐步把甲苯蒸出，缓慢升温至180℃，使三颈瓶中物料进行聚合反应，反应10h后，降温使体系冷却到室温，加入N,N-二甲基甲酰胺稀释，过滤除去不溶物；将滤液成细流装倒入快速搅拌的水中析出白色丝状聚合物；过滤收集聚合物，反复多次水洗，120℃真空烘干12h，得到含有叔胺侧基的酚酞聚芳醚砜。Add 0.1mol N,N-dimethylaminopropylamine into a three-necked flask equipped with a mechanical stirrer, a condenser and a water separator; feed ammonia gas into the three-necked flask, and slowly raise the temperature to 120°C to make the three-necked The materials in the neck bottle react to generate N-dimethylaminopropyl-3,3′-bis(4-hydroxyphenyl)benzopyrrolidone (PPH-TA); Add 0.1molPPH-TA, 0.1mol4,4'-dichlorodiphenyl sulfone, 0.2mol anhydrous potassium carbonate, 138mL dimethyl sulfoxide, 70mL toluene into the three-necked flask of the device; feed nitrogen into the three-necked flask, and Gradually raise the temperature of the three-necked bottle to 150°C, and reflux the toluene. After reflux for 4 hours, gradually distill the toluene out, slowly raise the temperature to 180°C, and polymerize the materials in the three-necked bottle. After 10 hours of reaction, lower the temperature to cool the system to room temperature , add N,N-dimethylformamide to dilute, filter to remove insoluble matter; pour the filtrate into thin streams into rapidly stirring water to precipitate white filamentous polymers; collect the polymers by filtration, wash repeatedly with water, and vacuum at 120°C Dry for 12 hours to obtain phenolphthalein polyarylethersulfone containing tertiary amine side groups.
结构测试结果表明，含有叔胺侧基的酚酞聚芳醚砜具有式（VI）所示结构。Structural test results show that the phenolphthalein polyarylethersulfone containing tertiary amine side groups has the structure shown in formula (VI).
实施例2Example 2
将100g实施例1制备的含叔胺侧基的酚酞聚芳醚砜（PES-TA）溶解于900g N,N-二甲基甲酰胺中，所述酚酞聚芳醚砜具有式（VI）所示结构，在60℃下加热搅拌溶解，搅拌速度为800r/min，得到质量浓度为10.00%的聚合物溶液；然后在所述聚合物溶液中加入5g1,3-环氧丙烷作为交联剂，在50℃下加热搅拌反应60min，得到制膜液；将所述制膜液过滤、脱泡后在刮膜机上刮膜，控制刮刀高度为200μm，制得超滤膜或纳滤膜前体；将所述超滤膜或纳滤膜前体在空气中静置20s后浸入水中固化24h，再在100℃下进一步固化交联，得到超滤膜或纳滤膜。Dissolve 100 g of phenolphthalein polyarylethersulfone (PES-TA) containing tertiary amine side groups prepared in Example 1 in 900 g of N,N-dimethylformamide, the phenolphthalein polyarylethersulfone having the formula (VI) The structure was shown, heated and stirred at 60°C to dissolve, the stirring speed was 800r/min, and a polymer solution with a mass concentration of 10.00% was obtained; then 5g of 1,3-propylene oxide was added to the polymer solution as a crosslinking agent, Heating and stirring at 50°C for 60 minutes to obtain a membrane-forming solution; after filtering and defoaming the membrane-forming solution, scrape the membrane on a film scraper, and control the height of the scraper to 200 μm to prepare an ultrafiltration membrane or nanofiltration membrane precursor; The ultrafiltration membrane or nanofiltration membrane precursor was left standing in the air for 20 seconds, then immersed in water for 24 hours to solidify, and then further solidified and cross-linked at 100° C. to obtain an ultrafiltration membrane or nanofiltration membrane.
本发明检测得到本实施例所制得的膜厚度80μm。The present invention detects that the thickness of the film prepared in this embodiment is 80 μm.
本发明将所制得的膜进行膜通量测试，采用乙醇作为测试液，按照上述技术方案所述的膜通量的测试方法，测试得到本实施例制备得到的膜的乙醇通量为219L/(m2·h)，In the present invention, the prepared membrane is tested for membrane flux, and ethanol is used as the test solution. According to the test method of the membrane flux described in the above technical scheme, the ethanol flux of the membrane prepared in this embodiment is 219L/ (m2 ·h),
本发明按照上述技术方案所述的膜截留率的测试方法，测试得到本发明实施例2得到的膜对罗丹明6B的截留率为99.8%。According to the test method of the membrane rejection rate described in the above-mentioned technical scheme, the present invention obtains a membrane rejection rate of 99.8% for Rhodamine 6B obtained in Example 2 of the present invention.
本发明按照上述技术方案所述的耐酸性的测试方法，测试结果如表4所示，表4为本发明实施例2得到的膜的耐酸性测试结果。The present invention follows the test method for acid resistance described in the technical solution above, and the test results are shown in Table 4. Table 4 is the test result of the acid resistance of the film obtained in Example 2 of the present invention.
表4本发明实施例2得到的膜的耐酸性测试结果The acid resistance test result of the membrane that table 4 embodiment of the present invention 2 obtains
由表4可以看出，本发明实施例2所得膜在HCl水溶液中浸泡72h后，膜的通量为209L/(m2·h)，膜对罗丹明6B的截留率为99.8%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐酸性。It can be seen from Table 4 that after the membrane obtained in Example 2 of the present invention was soaked in HCl aqueous solution for 72 hours, the flux of the membrane was 209 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.8%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better acid resistance.
本发明按照上述技术方案所述的耐碱性的测试方法，测试结果如表5所示，表5为本发明实施例2得到的膜的耐碱性测试结果。The present invention follows the test method for alkali resistance described in the technical solution above, and the test results are shown in Table 5, and Table 5 shows the test results of the alkali resistance of the film obtained in Example 2 of the present invention.
表5本发明实施例2得到的膜的耐碱性测试结果The alkali resistance test result of the film that the embodiment of the present invention 2 of table 5 obtains
由表5可以看出，本发明实施例2所得膜在NaOH水溶液中浸泡72h后，膜的通量为256L/(m2·h)，膜对罗丹明6B的截留率为99.5%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐碱性。It can be seen from Table 5 that after the membrane obtained in Example 2 of the present invention was soaked in NaOH aqueous solution for 72 hours, the flux of the membrane was 256 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.5%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better alkali resistance.
本发明按照上述技术方案所述的耐溶剂性的测试方法，测试结果如表6所示，表6为本发明实施例2得到的膜的耐溶剂性测试结果。The present invention follows the test method for solvent resistance described in the technical solution above, and the test results are shown in Table 6, and Table 6 shows the test results of the solvent resistance of the film obtained in Example 2 of the present invention.
表6本发明实施例2得到的膜的耐溶剂性测试结果The solvent resistance test result of the film that table 6 embodiment of the present invention 2 obtains
由表6可以看出，本发明实施例2所得膜在氯仿和N,N-二甲基甲酰胺中12h后，膜的通量分别为201L/(m2·h)和189L/(m2·h)，膜的截留率分别为99.9%和99.2%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐溶剂性。It can be seen from Table 6 that after the membrane obtained in Example 2 of the present invention was immersed in chloroform and N,N-dimethylformamide for 12 hours, the fluxes of the membrane were 201L/(m2 h) and 189L/(m2 h), the rejection rates of the membranes were 99.9% and 99.2%, respectively. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better solvent resistance.
实施例3Example 3
将100g实施例1制备的含叔胺侧基的酚酞聚芳醚砜（PES-TA）溶解于900g N,N-二甲基甲酰胺中，在60℃下加热搅拌溶解，搅拌速度为800r/min，得到质量浓度为10.0%的聚合物溶液；将聚合物溶液过滤、脱泡后在刮膜机上刮膜，控制刮刀高度为200μm，制得聚合物膜；将所得聚合物膜在空气中静置20s后浸入水中固化24h，得到初生膜；将初生膜浸入质量浓度为10%的1,2-二溴乙烷的乙醇溶液中，在50℃下反应60min后，再在100℃下进一步固化交联，得到超滤膜或纳滤膜。Dissolve 100g of phenolphthalein polyarylethersulfone (PES-TA) containing tertiary amine side groups prepared in Example 1 in 900g of N,N-dimethylformamide, heat and stir at 60°C to dissolve, and the stirring speed is 800r/ min to obtain a polymer solution with a mass concentration of 10.0%. After filtering the polymer solution and defoaming, scrape the film on a film scraper, and control the height of the scraper to 200 μm to obtain a polymer film; the obtained polymer film was statically placed in air Put it in water for 20s and then immerse in water to solidify for 24 hours to obtain a primary film; immerse the primary film in an ethanol solution of 1,2-dibromoethane with a mass concentration of 10%, react at 50°C for 60min, and then further solidify at 100°C Cross-linking to obtain ultrafiltration membrane or nanofiltration membrane.
本发明检测得到本实施例3得到的膜的厚度为80μm。The present invention detects that the thickness of the film obtained in Example 3 is 80 μm.
本发明按照上述技术方案所述的膜截留率的测试方法，测得膜的乙醇通量为232L/(m2·h);对罗丹明6B的截留率为99.7%。According to the test method of the membrane rejection rate described in the above technical scheme, the present invention measures that the ethanol flux of the membrane is 232L/(m2 h); the rejection rate of rhodamine 6B is 99.7%.
本发明按照上述技术方案所述的耐酸性的测试方法，测试结果如表7所示，表7为本发明实施例3得到的膜的耐酸性测试结果。The present invention follows the test method for acid resistance described in the technical solution above, and the test results are shown in Table 7. Table 7 shows the acid resistance test results of the film obtained in Example 3 of the present invention.
表7本发明实施例3得到的膜的耐酸性测试结果The acid resistance test result of the film that the embodiment of the present invention 3 of table 7 obtains
由表7可以看出，本实施例3所得膜在HCl水溶液中浸泡72h后，所得膜的通量为227L/(m2·h)，膜对罗丹明6B的截留率为99.6%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐酸性。It can be seen from Table 7 that after the membrane obtained in Example 3 was immersed in HCl aqueous solution for 72 hours, the flux of the obtained membrane was 227 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.6%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better acid resistance.
本发明按照上述技术方案所述的耐碱性的测试方法，测试结果如表8所示，表8为本发明实施例3得到的膜的耐碱性测试结果。The present invention follows the alkali resistance test method described in the above technical solution, and the test results are shown in Table 8, and Table 8 shows the alkali resistance test results of the membrane obtained in Example 3 of the present invention.
表8本发明实施例3得到的膜的耐碱性测试结果The alkali resistance test result of the film that the embodiment of the present invention 3 of table 8 obtains
由表8可以看出，本实施例3所得膜在NaOH水溶液中浸泡72h后，膜的通量为246L/(m2·h)，膜对罗丹明6B的截留率为99.5%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐碱性。It can be seen from Table 8 that after the membrane obtained in Example 3 was soaked in NaOH aqueous solution for 72 hours, the flux of the membrane was 246 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.5%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better alkali resistance.
本发明按照上述技术方案所述的耐溶剂性的测试方法，测试结果如表9所示，表9为本发明实施例3得到的膜的耐溶剂性测试结果。According to the test method of solvent resistance described in the technical solution of the present invention, the test results are shown in Table 9, and Table 9 shows the test results of the solvent resistance of the film obtained in Example 3 of the present invention.
表9本发明实施例3得到的膜的耐溶剂性测试结果The solvent resistance test result of the film that the embodiment of the present invention 3 of table 9 obtains
由表9可以看出，本实施例3所得膜在氯仿和N,N-二甲基甲酰胺中12h后，膜的通量分别为230L/(m2·h)和236L/(m2·h)，膜的截留率分别为99.7%和99.3%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐溶剂性。It can be seen from Table 9 that after the membrane obtained in Example 3 was immersed in chloroform and N,N-dimethylformamide for 12 hours, the fluxes of the membrane were 230L/(m2 ·h) and 236L/(m2 ·h) respectively. h), the rejection rates of the membranes were 99.7% and 99.3%, respectively. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better solvent resistance.
实施例4Example 4
将100g实施例1制备的含叔胺侧基的酚酞聚芳醚砜（PES-TA）溶解于900g N,N-二甲基甲酰胺中，在60℃下加热搅拌溶解，搅拌速度为800r/min，得到质量浓度为10.00%的聚合物溶液；将所述聚合物溶液过滤、脱泡后在刮膜机上刮膜，控制刮刀高度为200μm，得到聚合物膜；将所得聚合物膜在空气中静置20s后浸入水中固化24h，得到初生膜；将所述初生膜浸入浓度为10%的1,3-环氧丙烷的乙醇溶液中，在50℃下反应60min，再在100℃下进一步固化交联，得到超滤膜或纳滤膜。Dissolve 100g of phenolphthalein polyarylethersulfone (PES-TA) containing tertiary amine side groups prepared in Example 1 in 900g of N,N-dimethylformamide, heat and stir at 60°C to dissolve, and the stirring speed is 800r/ min to obtain a polymer solution with a mass concentration of 10.00%; after the polymer solution was filtered and defoamed, the film was scraped on a film scraper, and the height of the scraper was controlled to be 200 μm to obtain a polymer film; After standing for 20s, immerse in water to solidify for 24 hours to obtain a primary film; immerse the primary film in an ethanol solution of 1,3-propylene oxide with a concentration of 10%, react at 50°C for 60min, and then further solidify at 100°C Cross-linking to obtain ultrafiltration membrane or nanofiltration membrane.
本发明检测得到本实施例4所制得的膜的厚度为80μm。The present invention detects that the thickness of the film prepared in Example 4 is 80 μm.
本发明按照上述技术方案所述的膜截留率的测试方法，测得膜的乙醇通量为259L/(m2·h);对罗丹明6B的截留率为99.7%。According to the test method of the membrane rejection rate described in the above technical scheme, the present invention measures that the ethanol flux of the membrane is 259L/(m2 h); the rejection rate of rhodamine 6B is 99.7%.
本发明按照上述技术方案所述的耐酸性的测试方法，测试结果如表10所示，表10为本发明实施例4得到的膜的耐酸性测试结果。The present invention follows the test method for acid resistance described in the technical solution above, and the test results are shown in Table 10. Table 10 shows the test results of the acid resistance of the film obtained in Example 4 of the present invention.
表10本发明实施例4得到的膜的耐酸性测试结果The acid resistance test result of the membrane that table 10 embodiment of the present invention 4 obtains
由表10可以看出，本实施例4所得的膜在HCl水溶液中浸泡72h后，所得膜的通量为270L/(m2·h)，膜对罗丹明6B的截留率为99.5%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐酸性。It can be seen from Table 10 that after the membrane obtained in Example 4 was soaked in HCl aqueous solution for 72 hours, the flux of the obtained membrane was 270 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.5%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better acid resistance.
本发明按照上述技术方案所述的耐碱性的测试方法，测试结果如表11所示，表11为本发明实施例4得到的膜的耐碱性测试结果。The present invention follows the alkali resistance test method described in the above technical solution, and the test results are shown in Table 11. Table 11 shows the alkali resistance test results of the membrane obtained in Example 4 of the present invention.
表11本发明实施例4得到的膜的耐碱性测试结果The alkali resistance test result of the membrane that table 11 embodiment 4 of the present invention obtains
由表11可以看出，本实施例4所得的膜在NaOH水溶液中浸泡72h后，膜的通量为289L/(m2·h)，膜对罗丹明6B的截留率为99.4%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐碱性。It can be seen from Table 11 that after the membrane obtained in Example 4 was immersed in NaOH aqueous solution for 72 hours, the flux of the membrane was 289 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.4%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better alkali resistance.
本发明按照上述技术方案所述的耐溶剂性的测试方法，测试结果如表12所示，表12为本发明实施例4得到的膜的耐溶剂性测试结果。The present invention follows the test method for solvent resistance described in the technical solution above, and the test results are shown in Table 12. Table 12 shows the test results of the solvent resistance of the film obtained in Example 4 of the present invention.
表12本发明实施例4得到的膜的耐溶剂性测试结果The solvent resistance test result of the film that table 12 embodiment 4 of the present invention obtains
由表12可以看出，本实施例4所得膜在氯仿和N,N-二甲基甲酰胺中12h后，膜的通量分别为253L/(m2·h)和272L/(m2·h)，膜的截留率分别为99.7%和99.3%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐溶剂性。It can be seen from Table 12 that after the membrane obtained in Example 4 was immersed in chloroform and N,N-dimethylformamide for 12 hours, the fluxes of the membrane were 253L/(m2 ·h) and 272L/(m2 ·h) respectively. h), the rejection rates of the membranes were 99.7% and 99.3%, respectively. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better solvent resistance.
实施例5Example 5
将4,4′-联苯二酚11.0g(0.10mol)溶于100mL无水乙醇中，在氮气保护和搅拌条件下加入二甲胺水溶液(6.0equiv.,33%)和甲醛水溶液(8.0equiv.,37%)，然后室温搅拌48h。反应过程中，析出大量白色固体产物，过滤后，用乙醇重结晶，干燥得到白色粉末即为3，3’,5，5’-四（二甲基胺基）甲基-联苯二酚单体（TDMMB），收率为65%。Dissolve 11.0 g (0.10 mol) of 4,4'-biphenyldiphenol in 100 mL of absolute ethanol, add aqueous dimethylamine (6.0 equiv., 33%) and aqueous formaldehyde (8.0 equiv. .,37%), then stirred at room temperature for 48h. During the reaction process, a large amount of white solid product was precipitated, after filtration, recrystallized with ethanol, and dried to obtain a white powder which was 3,3',5,5'-tetrakis(dimethylamino)methyl-biphenyldiphenol Body (TDMMB), the yield is 65%.
在装有机械搅拌、冷凝器和分水器的三颈瓶中加入0.1mol TDMMB，0.1mol4,4′-二氯二苯砜，0.2mol无水碳酸钾、138mL二甲亚砜、70mL甲苯；向三颈瓶中通入氮气，并将三颈瓶逐渐升温至150℃，使甲苯回流，回流4h后，逐步把甲苯蒸出，缓慢升温至180℃，使三颈瓶中物料进行聚合反应，反应10h后，降温使体系冷却到室温，加入N,N-二甲基甲酰胺稀释，过滤除去不溶物；将滤液成细流装倒入快速搅拌的水中析出白色丝状聚合物；过滤收集聚合物，反复多次水洗，120℃真空烘干12h，得到主链含叔胺基团的聚芳醚砜。Add 0.1mol TDMMB, 0.1mol 4,4′-dichlorodiphenyl sulfone, 0.2mol anhydrous potassium carbonate, 138mL dimethyl sulfoxide, and 70mL toluene to a three-necked flask equipped with mechanical stirring, condenser and water separator; Introduce nitrogen into the three-necked bottle, and gradually raise the temperature of the three-necked bottle to 150°C, and reflux the toluene. After reflux for 4 hours, gradually distill the toluene out, slowly raise the temperature to 180°C, and polymerize the materials in the three-necked bottle. After reacting for 10 hours, lower the temperature to cool the system to room temperature, add N,N-dimethylformamide to dilute, and filter to remove insoluble matter; pour the filtrate into thin streams into rapidly stirring water to precipitate white filamentous polymers; collect the polymer by filtration The product was washed with water several times, and vacuum-dried at 120°C for 12 hours to obtain polyarylethersulfone with a main chain containing tertiary amine groups.
结构测试结果表明，主链含叔胺基团的聚芳醚砜具有式（VII）所示结构。Structural test results show that the polyarylethersulfone with tertiary amino groups in the main chain has the structure shown in formula (VII).
实施例6Example 6
将100g实施例5制备的主链含叔胺基团的聚芳醚砜（T-PES）溶解于900gN,N-二甲基甲酰胺中，所述聚芳醚砜具有式（VII）所示结构，在60℃下加热搅拌溶解，搅拌速度为800r/min，得到质量浓度为10.00%的聚合物溶液；然后在所述聚合物溶液中加入5g1,3-环氧丙烷作为交联剂，在50℃下加热搅拌反应60min，得到制膜液；将所述制膜液过滤、脱泡后在刮膜机上刮膜，控制刮刀高度为200μm，得到超滤膜或纳滤膜前体；将得到的超滤膜或纳滤膜前体在空气中静置20s后，浸入水中固化24h；再在100℃下进一步固化交联，得到超滤膜或纳滤膜。Dissolve 100 g of the polyarylethersulfone (T-PES) containing tertiary amino groups in the main chain prepared in Example 5 in 900 g of N,N-dimethylformamide. The polyarylethersulfone has the formula (VII) structure, heated and stirred at 60°C to dissolve, and the stirring speed was 800r/min to obtain a polymer solution with a mass concentration of 10.00%; then 5g of 1,3-propylene oxide was added to the polymer solution as a crosslinking agent, and Heating and stirring at 50°C for 60 minutes to obtain a membrane-forming solution; after filtering and defoaming the membrane-forming solution, scrape the film on a film scraper, and control the height of the scraper to 200 μm to obtain an ultrafiltration membrane or nanofiltration membrane precursor; After standing in the air for 20s, the ultrafiltration membrane or nanofiltration membrane precursor was immersed in water for 24 hours to solidify; and then further solidified and cross-linked at 100°C to obtain an ultrafiltration membrane or nanofiltration membrane.
本发明检测得到本实施例6所制得的膜的厚度为60μm。The present invention detects that the thickness of the film prepared in Example 6 is 60 μm.
本发明按照上述技术方案所述的膜截留率的测试方法，测得膜的乙醇通量为292L/(m2·h);对罗丹明6B的截留率为99.7%。According to the test method of the membrane rejection rate described in the above technical scheme, the present invention measures that the ethanol flux of the membrane is 292L/(m2 ·h); the rejection rate of rhodamine 6B is 99.7%.
本发明按照上述技术方案所述的耐酸性的测试方法，测试结果如表13所示，表13为本发明实施例6得到的膜的耐酸性测试结果。The present invention follows the test method for acid resistance described in the technical solution above, and the test results are shown in Table 13. Table 13 shows the acid resistance test results of the film obtained in Example 6 of the present invention.
表13本发明实施例6得到的膜的耐酸性测试结果The acid resistance test result of the membrane that table 13 embodiment 6 of the present invention obtains
由表13可以看出，本实施例6所得的膜在HCl水溶液中浸泡72h后，所得膜的通量为272L/(m2·h)，膜对罗丹明6B的截留率为99.8%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐酸性。It can be seen from Table 13 that after the membrane obtained in Example 6 was soaked in HCl aqueous solution for 72 hours, the flux of the obtained membrane was 272 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.8%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better acid resistance.
本发明按照上述技术方案所述的耐碱性的测试方法，测试结果如表14所示，表14为本发明实施例6得到的膜的耐碱性测试结果。The present invention follows the test method for alkali resistance described in the technical solution above, and the test results are shown in Table 14. Table 14 shows the test results of the alkali resistance of the film obtained in Example 6 of the present invention.
表14本发明实施例6得到的膜的耐碱性测试结果The alkali resistance test result of the membrane that table 14 embodiment of the present invention 6 obtains
由表10可以看出，本实施例6所得膜在NaOH水溶液中浸泡72h后，膜的通量为279L/(m2·h)，膜对罗丹明6B的截留率为99.4%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐碱性。It can be seen from Table 10 that after the membrane obtained in Example 6 was soaked in NaOH aqueous solution for 72 hours, the flux of the membrane was 279 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.4%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better alkali resistance.
本发明按照上述技术方案所述的耐溶剂性的测试方法，测试结果如表15所示，表15为本发明实施例6得到的膜的耐溶剂性测试结果。The present invention follows the test method for solvent resistance described in the technical solution above, and the test results are shown in Table 15, and Table 15 shows the test results of the solvent resistance of the film obtained in Example 6 of the present invention.
表15本发明实施例6得到的膜的耐溶剂性测试结果The solvent resistance test result of the film that table 15 embodiment 6 of the present invention obtains
由表15可以看出，本实施例6所得膜在氯仿和N,N-二甲基甲酰胺中12h后，膜的通量分别为279L/(m2·h)和288L/(m2·h)，膜的截留率分别为99.9%和99.6%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐溶剂性。It can be seen from Table 15 that after the membrane obtained in Example 6 was immersed in chloroform and N,N-dimethylformamide for 12 hours, the fluxes of the membrane were 279L/(m2 ·h) and 288L/(m2 ·h) respectively. h), the rejection rates of the membranes are 99.9% and 99.6%, respectively. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better solvent resistance.
实施例7Example 7
将100g实施例5制备的主链含叔胺基团的聚芳醚砜（T-PES）溶解于900g N,N-二甲基甲酰胺中，在60℃下加热搅拌溶解，搅拌速度为800r/min，得到质量浓度为10.00%的聚合物溶液；将所述聚合物溶液过滤、脱泡后在刮膜机上刮膜，控制刮刀高度为200μm，得到聚合物膜；将所述聚合物膜在空气中静置20s后，浸入水中固化24h，得到初生膜；然后将所得初生膜浸入浓度为10%的1,3-环氧丙烷的乙醇溶液中，在50℃下加热反应60min后，再在100℃下进一步固化交联，得到超滤膜或纳滤膜。Dissolve 100g of polyarylethersulfone (T-PES) containing tertiary amino groups in the main chain prepared in Example 5 in 900g of N,N-dimethylformamide, heat and stir at 60°C to dissolve, and the stirring speed is 800r /min to obtain a polymer solution with a mass concentration of 10.00%; after the polymer solution is filtered and defoamed, the film is scraped on a film scraper, and the height of the scraper is controlled to be 200 μm to obtain a polymer film; After standing in the air for 20s, immerse in water to solidify for 24 hours to obtain a primary film; then immerse the resulting primary film in a 10% ethanol solution of 1,3-propylene oxide, heat and react at 50°C for 60 minutes, and then The cross-linking is further solidified at 100°C to obtain an ultrafiltration membrane or a nanofiltration membrane.
本发明检测得到本实施例7所制得的膜的厚度为60μm。The present invention detects that the thickness of the film prepared in Example 7 is 60 μm.
本发明按照上述技术方案所述的膜截留率的测试方法，测得膜的乙醇通量为286L/(m2·h)；对罗丹明6B的截留率为99.8%。According to the test method of the membrane rejection rate described in the technical scheme, the ethanol flux of the membrane is measured to be 286L/(m2 ·h); the rejection rate of rhodamine 6B is 99.8%.
本发明按照上述技术方案所述的耐酸性的测试方法，测试结果如表16所示，表16为本发明实施例7得到的膜的耐酸性测试结果。The present invention follows the test method for acid resistance described in the technical solution above, and the test results are shown in Table 16. Table 16 shows the acid resistance test results of the film obtained in Example 7 of the present invention.
表16本发明实施例7得到的膜的耐酸性测试结果The acid resistance test result of the membrane that table 16 embodiment of the present invention 7 obtains
由表16可以看出，本实施例7所得的膜在HCl水溶液中浸泡72h后，所得膜的通量为276L/(m2·h)，膜对罗丹明6B的截留率为99.8%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐酸性。It can be seen from Table 16 that after the membrane obtained in Example 7 was immersed in HCl aqueous solution for 72 hours, the flux of the obtained membrane was 276 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.8%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better acid resistance.
本发明按照上述技术方案所述的耐碱性的测试方法，测试结果如表17所示，表17为本发明实施例7得到的膜的耐碱性测试结果。The present invention follows the test method for alkali resistance described in the technical solution above, and the test results are shown in Table 17. Table 17 shows the test results of the alkali resistance of the film obtained in Example 7 of the present invention.
表17本发明实施例7得到的膜的耐碱性测试结果The alkali resistance test result of the membrane that table 17 embodiment of the present invention 7 obtains
由表17可以看出，本实施例7所得膜在NaOH水溶液中浸泡72h后，膜的通量为215L/(m2·h)，膜对罗丹明6B的截留率为99.4%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐碱性。It can be seen from Table 17 that after the membrane obtained in Example 7 was immersed in NaOH aqueous solution for 72 hours, the flux of the membrane was 215 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.4%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better alkali resistance.
本发明按照上述技术方案所述的耐溶剂性的测试方法，测试结果如表18所示，表18为本发明实施例7得到的膜的耐溶剂性测试结果。According to the test method of solvent resistance described in the technical solution of the present invention, the test results are shown in Table 18, and Table 18 shows the test results of the solvent resistance of the film obtained in Example 7 of the present invention.
表18本发明实施例7得到的膜的耐溶剂性测试结果The solvent resistance test result of the film that the embodiment of the present invention 7 of table 18 obtains
由表18可以看出，本实施例7所得膜在氯仿和N,N-二甲基甲酰胺中12h后，膜的通量分别为279L/(m2·h)和288L/(m2·h)，膜的截留率分别为99.9%和99.8%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐溶剂性。It can be seen from Table 18 that after the membrane obtained in Example 7 was immersed in chloroform and N,N-dimethylformamide for 12 hours, the fluxes of the membrane were 279L/(m2 ·h) and 288L/(m2 ·h) respectively. h), the rejection rates of the membranes are 99.9% and 99.8%, respectively. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better solvent resistance.
实施例8Example 8
将100g实施例5制备的主链含叔胺基团的聚芳醚砜（PES-TA）溶解于900g N,N-二甲基甲酰胺中，在60℃下加热搅拌溶解，搅拌速度为800r/min，得到质量浓度为10.00%的聚合物溶液；然后在所述聚合物溶液中加入5g1,3-环氧丙烷作为交联剂，在50℃下加热搅拌反应60min，得到制膜液；将所述制膜液过滤、脱泡后在刮膜机上刮膜，控制刮刀高度为200μm，制得滤膜；将所述滤膜在空气中静置20s后，浸入水中固化24h，得到超滤膜或纳滤膜。Dissolve 100g of polyarylethersulfone (PES-TA) containing tertiary amino groups in the main chain prepared in Example 5 in 900g of N,N-dimethylformamide, heat and stir at 60°C to dissolve, and the stirring speed is 800r /min to obtain a polymer solution with a mass concentration of 10.00%; then add 5g of 1,3-propylene oxide as a crosslinking agent in the polymer solution, and heat and stir at 50°C for 60 minutes to obtain a film-making solution; After the membrane-making liquid is filtered and defoamed, the membrane is scraped on a scraping machine, and the height of the scraper is controlled to be 200 μm to obtain a filter membrane; after the filter membrane is left to stand in the air for 20 seconds, it is immersed in water to solidify for 24 hours to obtain an ultrafiltration membrane or nanofiltration membranes.
本发明检测得到本实施例8所制得的膜厚度80μm。The present invention detects that the thickness of the film prepared in Example 8 is 80 μm.
本发明按照上述技术方案所述的膜截留率的测试方法，测得膜的乙醇通量为306L/(m2·h);对罗丹明6B的截留率为99.7%。According to the test method of the membrane rejection rate described in the above technical scheme, the present invention measures that the ethanol flux of the membrane is 306 L/(m2 h); the rejection rate of Rhodamine 6B is 99.7%.
本发明按照上述技术方案所述的耐酸性的测试方法，测试结果如表19所示，表19为本发明实施例8得到的膜的耐酸性测试结果。The present invention follows the acid resistance test method described in the technical solution above, and the test results are shown in Table 19, which is the acid resistance test result of the film obtained in Example 8 of the present invention.
表19本发明实施例8得到的膜的耐酸性测试结果The acid resistance test result of the membrane that table 19 embodiment 8 of the present invention obtains
由表19可以看出，本实施例8所得的膜在HCl水溶液中浸泡72h后，所得膜的通量为283L/(m2·h)，膜对罗丹明6B的截留率为99.8%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐酸性。It can be seen from Table 19 that after the membrane obtained in Example 8 was immersed in HCl aqueous solution for 72 hours, the flux of the obtained membrane was 283 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.8%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better acid resistance.
本发明按照上述技术方案所述的耐碱性的测试方法，测试结果如表20所示，表20为本发明实施例8得到的膜的耐碱性测试结果。The present invention follows the alkali resistance test method described in the above technical solution, and the test results are shown in Table 20, which is the alkali resistance test result of the film obtained in Example 8 of the present invention.
表20本发明实施例8得到的膜的耐碱性测试结果The alkali resistance test result of the membrane that table 20 embodiment of the present invention 8 obtains
由表20可以看出，本实施例8所得膜在NaOH水溶液中浸泡72h后，膜的通量为324L/(m2·h)，膜对罗丹明6B的截留率为99.6%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐碱性。It can be seen from Table 20 that after the membrane obtained in Example 8 was soaked in NaOH aqueous solution for 72 hours, the flux of the membrane was 324 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.6%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better alkali resistance.
本发明按照上述技术方案所述的耐溶剂性的测试方法，测试结果如表21所示，表21为本发明实施例8得到的膜的耐溶剂性测试结果。The present invention follows the test method for solvent resistance described in the technical solution above, and the test results are shown in Table 21. Table 21 shows the test results of the solvent resistance of the film obtained in Example 8 of the present invention.
表21本发明实施例8得到的膜的耐溶剂性测试结果The solvent resistance test result of the film that table 21 embodiment of the present invention 8 obtains
由表21可以看出，本实施例8所得膜在氯仿和N,N-二甲基甲酰胺中12h后，膜的通量分别为284L/(m2·h)和272L/(m2·h)，膜的截留率分别为99.6%和99.8%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐溶剂性。It can be seen from Table 21 that after the membrane obtained in Example 8 was immersed in chloroform and N,N-dimethylformamide for 12 hours, the fluxes of the membrane were 284L/(m2 ·h) and 272L/(m2 ·h) respectively. h), the rejection rates of the membranes were 99.6% and 99.8%, respectively. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better solvent resistance.
实施例9Example 9
将100g实施例5制备的主链含叔胺基团的聚芳醚砜（PES-TA）溶解于900g N,N-二甲基甲酰胺中，在60℃下加热搅拌溶解，搅拌速度为800r/min，得到质量浓度为10.00%的聚合物溶液；然后将所述制膜液过滤、脱泡后在刮膜机上刮膜，控制刮刀高度为200μm，制得聚合物膜；将所述聚合物膜在空气中静置20s后，再浸入浓度为10%的1,3-环氧丙烷的乙醇溶液中发生交联反应并固化，得到超滤膜或纳滤膜。Dissolve 100g of polyarylethersulfone (PES-TA) containing tertiary amino groups in the main chain prepared in Example 5 in 900g of N,N-dimethylformamide, heat and stir at 60°C to dissolve, and the stirring speed is 800r /min to obtain a polymer solution with a mass concentration of 10.00%; then filter the film-making solution and defoam and scrape the film on a film scraper to control the height of the scraper to 200 μm to obtain a polymer film; After the membrane was left to stand in the air for 20 seconds, it was immersed in a 10% ethanol solution of 1,3-propylene oxide to undergo a cross-linking reaction and solidify to obtain an ultrafiltration membrane or a nanofiltration membrane.
本发明检测得到本实施例所制得的膜厚度80μm。The present invention detects that the thickness of the film prepared in this embodiment is 80 μm.
本发明按照上述技术方案所述的膜截留率的测试方法，测得膜的乙醇通量为342L/(m2·h);对罗丹明6B的截留率为99.8%。According to the test method of the membrane rejection rate described in the above technical scheme, the present invention measures that the ethanol flux of the membrane is 342L/(m2 h); the rejection rate of rhodamine 6B is 99.8%.
本发明按照上述技术方案所述的耐酸性的测试方法，测试结果如表22所示，表22为本发明实施例9得到的膜的耐酸性测试结果。The present invention follows the test method for acid resistance described in the technical solution above, and the test results are shown in Table 22. Table 22 shows the acid resistance test results of the film obtained in Example 9 of the present invention.
表22本发明实施例9得到的膜的耐酸性测试结果The acid resistance test result of the membrane that table 22 embodiment of the present invention 9 obtains
由表22可以看出，本实施例9所得的膜在HCl水溶液中浸泡72h后，所得膜的通量为342L/(m2·h)，膜对罗丹明6B的截留率为99.7%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐酸性。It can be seen from Table 22 that after the membrane obtained in Example 9 was immersed in HCl aqueous solution for 72 hours, the flux of the obtained membrane was 342 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.7%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better acid resistance.
本发明按照上述技术方案所述的耐碱性的测试方法，测试结果如表23所示，表23为本发明实施例9得到的膜的耐碱性测试结果。The present invention follows the test method for alkali resistance described in the technical solution above, and the test results are shown in Table 23, and Table 23 shows the test results of the alkali resistance of the film obtained in Example 9 of the present invention.
表23本发明实施例9得到的膜的耐碱性测试结果The alkali resistance test result of the membrane that table 23 embodiment 9 of the present invention obtains
由表23可以看出，本实施例9所得膜在NaOH水溶液中浸泡72h后，膜的通量为374L/(m2·h)，膜对罗丹明6B的截留率为99.6%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐碱性。It can be seen from Table 23 that after the membrane obtained in Example 9 was immersed in NaOH aqueous solution for 72 hours, the flux of the membrane was 374 L/(m2 ·h), and the rejection rate of rhodamine 6B by the membrane was 99.6%. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better alkali resistance.
本发明按照上述技术方案所述的耐溶剂性的测试方法，测试结果如表24所示，表24为本发明实施例9得到的膜的耐溶剂性测试结果。The present invention follows the solvent resistance test method described in the technical solution above, and the test results are shown in Table 24, which shows the solvent resistance test results of the film obtained in Example 9 of the present invention.
表24本发明实施例9得到的膜的耐溶剂性测试结果The solvent resistance test result of the membrane that table 24 embodiment of the present invention 9 obtains
由表24可以看出，本实施例9所得膜在氯仿和N,N-二甲基甲酰胺中12h后，膜的通量分别为340L/(m2·h)和318L/(m2·h)，膜的截留率分别为99.6%和99.8%。由此可以看出，与比较例1相比，本发明提供的制备方法得到的超滤膜或纳滤膜具有较好的耐溶剂性。It can be seen from Table 24 that after the membrane obtained in Example 9 was immersed in chloroform and N,N-dimethylformamide for 12 hours, the fluxes of the membrane were 340L/(m2 ·h) and 318L/(m2 ·h) respectively. h), the rejection rates of the membranes were 99.6% and 99.8%, respectively. It can be seen that, compared with Comparative Example 1, the ultrafiltration membrane or nanofiltration membrane obtained by the preparation method provided by the present invention has better solvent resistance.
由以上实施例可知，本发明提供了一种超滤膜或纳滤膜及其制备方法，本发明采用如式（I）或式（II）所示结构的化合物作为制膜聚合物，该聚合物中含有可交联的叔胺基团，在20℃～150℃下，易与交联剂发生交联反应，得到网状结构的交联产物，在膜中同样形成网状的结构，使所得超滤膜或纳滤膜在酸性和碱性溶液中呈现不溶不融的现象。因此，通过本发明提供的方法制备的超滤膜或纳滤膜在酸性和碱性环境中具有良好的稳定性。另外，本发明提供的方法得到的超滤膜或纳滤膜还具有较好的耐溶剂性。As can be seen from the above examples, the present invention provides an ultrafiltration membrane or a nanofiltration membrane and a preparation method thereof. The present invention uses a compound having a structure shown in formula (I) or formula (II) as a membrane-forming polymer, and the polymerization The product contains cross-linkable tertiary amine groups, and at 20°C to 150°C, it is easy to undergo a cross-linking reaction with a cross-linking agent to obtain a cross-linked product with a network structure, which also forms a network structure in the film. The obtained ultrafiltration membrane or nanofiltration membrane is insoluble and infusible in acidic and alkaline solutions. Therefore, the ultrafiltration membrane or nanofiltration membrane prepared by the method provided by the invention has good stability in acidic and alkaline environments. In addition, the ultrafiltration membrane or nanofiltration membrane obtained by the method provided by the invention also has better solvent resistance.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310355792.XACN103386255B (en) | 2013-08-15 | 2013-08-15 | A kind of milipore filter or NF membrane and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310355792.XACN103386255B (en) | 2013-08-15 | 2013-08-15 | A kind of milipore filter or NF membrane and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN103386255A CN103386255A (en) | 2013-11-13 |
| CN103386255Btrue CN103386255B (en) | 2015-08-05 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310355792.XAActiveCN103386255B (en) | 2013-08-15 | 2013-08-15 | A kind of milipore filter or NF membrane and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN103386255B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104132908A (en)* | 2014-07-04 | 2014-11-05 | 郑州轻工业学院 | Method for determining equilibrium moisture content of tobacco leaf |
| CN104096484B (en)* | 2014-08-11 | 2017-01-11 | 中国科学院长春应用化学研究所 | Ultrafiltration membrane and preparation method thereof |
| CN104190265A (en)* | 2014-08-31 | 2014-12-10 | 浙江大学 | Low-pressure high-flux chlorine-containing polymer nanofiltration membrane with stable separation layer and preparation method thereof |
| CN105435644A (en)* | 2014-09-29 | 2016-03-30 | 中国石油化工股份有限公司 | Nanofiltration membrane and preparation method thereof |
| CN104892925B (en)* | 2015-05-29 | 2017-11-28 | 中国科学院长春应用化学研究所 | A kind of preparation method of quaternary amine fluidized polymer, NF membrane and NF membrane |
| CN106378016B (en)* | 2016-02-29 | 2019-11-15 | 深港产学研基地 | Nanofiltration membrane and its preparation method and application |
| CN110180412A (en)* | 2019-05-29 | 2019-08-30 | 浙江工业大学 | A kind of preparation method of acid resistance Nano filtering composite membrane |
| CN111569680B (en)* | 2020-06-02 | 2021-03-19 | 四川大学 | Polyarylether ultrafiltration membrane, nanofiltration membrane, preparation method and method for reversible conversion of ultrafiltration membrane and nanofiltration membrane |
| CN113563576A (en)* | 2021-07-26 | 2021-10-29 | 中国科学院长春应用化学研究所 | A kind of method for rapidly preparing tertiary amine polymer |
| CN113952846B (en)* | 2021-10-14 | 2024-01-26 | 天津工业大学 | Heat-resistant zwitterionic polyether-ether-ketone loose nanofiltration membrane and preparation method and application thereof |
| CN115414803B (en)* | 2022-10-14 | 2024-03-26 | 中国科学院过程工程研究所 | Acid-resistant polyimide ultrafiltration membrane and its preparation method and application |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704946A (en)* | 2009-12-21 | 2010-05-12 | 中国科学院长春应用化学研究所 | Polyarylether containing quaternary ammonium side groups and preparation method thereof |
| CN101724153A (en)* | 2009-12-16 | 2010-06-09 | 中国科学院长春应用化学研究所 | A kind of phenolphthalein polyethersulfone containing tertiary amine side group and preparation method thereof |
| CN102698617A (en)* | 2012-06-08 | 2012-10-03 | 厦门大学 | Acid-alkali polymer blend pervaporation membrane, and preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289305B (en)* | 2009-01-13 | 2018-03-30 | Ams技术Int（2012）有限公司 | For metal ion and liquid to be processed to the solvent and the stable film of acid, apparatus and method of flow separation |
| WO2010095139A1 (en)* | 2009-02-19 | 2010-08-26 | Ben-Gurion University Of The Negev Research And Development Authority | Chemically resistant membranes, coatings and films and methods for their preparation |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724153A (en)* | 2009-12-16 | 2010-06-09 | 中国科学院长春应用化学研究所 | A kind of phenolphthalein polyethersulfone containing tertiary amine side group and preparation method thereof |
| CN101704946A (en)* | 2009-12-21 | 2010-05-12 | 中国科学院长春应用化学研究所 | Polyarylether containing quaternary ammonium side groups and preparation method thereof |
| CN102698617A (en)* | 2012-06-08 | 2012-10-03 | 厦门大学 | Acid-alkali polymer blend pervaporation membrane, and preparation method and application thereof |
| Publication number | Publication date |
|---|---|
| CN103386255A (en) | 2013-11-13 |
| Publication | Publication Date | Title |
|---|---|---|
| CN103386255B (en) | A kind of milipore filter or NF membrane and preparation method thereof | |
| CN111514768B (en) | Solvent-resistant polymer nanofiltration membrane and preparation method and application thereof | |
| EP2857087A1 (en) | Reverse osmosis membrane | |
| CN102824859B (en) | Method for preparing hollow fiber nanofiltration membrane by using thermally induced phase separation/interface cross linking synchronization method | |
| EP2857088A1 (en) | Method for manufacturing a reverse osmosis membrane and a reverse osmosis membrane manufactured thereby | |
| CN108355498B (en) | Negatively charged composite nanofiltration membrane and preparation method thereof | |
| CN102527265B (en) | Membrane functional monomer containing hexafluoroisopropanol group and preparation method of nanofiltration membrane thereof | |
| CN108499361B (en) | Preparation method of nano-porous polymer film with adjustable pore size | |
| CN106693706A (en) | Nanofiltration membrane, and preparation method and application thereof | |
| CN110052178B (en) | High-tolerance organic solvent separation membrane and preparation method thereof | |
| CN111378204B (en) | Preparation method and application of polyethyleneimine sponge loaded with COF-LZU1 | |
| CN101721927B (en) | Copolyaryl ether sulfone ultrafiltration membrane containing phthalazinone structure and preparation method thereof | |
| CN111921383A (en) | Preparation method of triazine porous organic nanoparticle-based assembled film | |
| CN115554849A (en) | A preparation method of polyethyleneimine-based positively charged nanofiltration membrane | |
| CN105709616A (en) | Method for preparing organic-solvent-resistant ultrafiltration membrane, prepared ultrafiltration membrane and application of ultrafiltration membrane | |
| CN101721926B (en) | Sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone and preparation method thereof | |
| CN110559884A (en) | MIL-101@ PIM-1 composite pervaporation membrane and preparation method and application thereof | |
| JP4057217B2 (en) | Method for producing solvent-resistant microporous polybenzimidazole thin film | |
| CN114247299B (en) | Preparation method of solvent-resistant composite nanofiltration membrane | |
| CN116637506A (en) | Catalytic self-cleaning internal pressure type composite nanofiltration membrane and preparation method and application thereof | |
| CN105233703A (en) | Preparation method of high flux cellulose microfiltration membrane | |
| CN107638813A (en) | A kind of preparation method and applications of doughnut solvent resistant NF membrane | |
| CN113842783B (en) | An acid-resistant high-flux polyarylene ether composite nanofiltration membrane, preparation method and application | |
| CN1235669C (en) | Separation membrane made from cellulose and its preparing method | |
| CN118320644A (en) | Organic solvent-resistant separation membrane and preparation method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | Application publication date:20131113 Assignee:Shandong Zhongke Precision Film Environmental Protection New Materials Co.,Ltd. Assignor:CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY CHINESE ACADEMY OF SCIENCES Contract record no.:X2024990000297 Denomination of invention:A ultrafiltration membrane or nanofiltration membrane and its preparation method Granted publication date:20150805 License type:Exclusive License Record date:20240620 | |
| EE01 | Entry into force of recordation of patent licensing contract |